Processes for preparing hydroxides and oxides of various metals and derivatives thereof

ABSTRACT

There are provided processes for preparing a metal hydroxide comprising (i) at least one metal chosen from nickel and cobalt and optionally (ii) at least one metal chosen from manganese, lithium and aluminum, the process comprising reacting a metal sulfate comprising (i) at least one metal chosen from nickel and cobalt and optionally (ii) at least one metal chosen from manganese, lithium and aluminum with lithium hydroxide, sodium hydroxide and/or potassium hydroxide and optionally a chelating agent in order to obtain a solid comprising the metal hydroxide and a liquid comprising lithium sulfate, sodium sulfate and/or potassium sulfate: separating the liquid and the solid from one another to obtain the metal hydroxide; submitting the liquid comprising lithium sulfate, sodium sulfate and/or potassium sulfate to an electromembrane process for converting the lithium sulfate, sodium sulfate and/or potassium sulfate into lithium hydroxide, sodium hydroxide and/or potassium hydroxide respectively; reusing the sodium hydroxide obtained by the electromembrane process for reacting with the metal sulfate; and reusing the lithium hydroxide obtained by the electromembrane process for reacting with the metal sulfate and/or with the metal hydroxide.

CROSS-REFERENCE TO RELATES APPLICATIONS

The present disclosure claims priority to U.S. application No.62/590,260 filed and Nov. 22, 2017; and to U.S. application No.62/735,013 filed and Sep. 21, 2018. These documents are herebyincorporated by reference in their entirety.

TECHNICAL FIELD

The present disclosure relates to improvements in the field of processesfor preparing metal hydroxides and metal oxides that contain at leastone metal chosen from nickel, cobalt, manganese, lithium and aluminum.For example, such material can be useful in the manufacture of cathodematerials for ion batteries.

BACKGROUND OF THE DISCLOSURE

Processes for preparing nickel-cobalt-manganese hydroxides,nickel-cobalt-aluminum hydroxides, lithium-cobalt hydroxides,nickel-cobalt-manganese oxyhydroxides, nickel-cobalt-aluminumoxyhydroxides, lithium cobalt oxyhydroxides, nickel-cobalt-manganeseoxides, nickel-cobalt-aluminum oxides and lithium-cobalt oxides areknown. However, processes known for example lead to high costs in theproduction of such hydroxides and oxides as well as consumption ofvarious chemicals.

There is thus a need for at least an alternative process for preparingsuch hydroxides or oxides.

SUMMARY OF THE DISCLOSURE

Therefore according to an aspect of the present disclosure, there isprovided a process for preparing a metal, hydroxide comprising (i) atleast one metal chosen from nickel and cobalt and optionally (ii) atleast one metal chosen from manganese, lithium and aluminum, the processcomprising:

reacting a metal sulfate comprising (i) at least one metal chosen fromnickel and cobalt and optionally (ii) at least one metal chosen frommanganese, lithium and aluminum with lithium hydroxide and optionally achelating agent in order to obtain a solid comprising the metalhydroxide and a liquid comprising lithium sulfate;

separating the liquid and the solid from one another to obtain the metalhydroxide;

submitting the liquid comprising lithium sulfate to an electromembraneprocess for converting the lithium sulfate into lithium hydroxide; and

reusing the lithium hydroxide obtained by the electromembrane processfor reacting with the metal sulfate.

According to another aspect, there is provided a process for preparing ametal oxide comprising (i) at least one metal chosen from nickel andcobalt and optionally (ii) at least one metal chosen from manganese,lithium and aluminum, the process comprising:

reacting a metal sulfate comprising (i) at least one metal chosen fromnickel and cobalt and optionally (ii) at least one metal chosen frommanganese, lithium and aluminum with lithium hydroxide and optionally achelating agent to obtain a solid comprising a metal hydroxidecomprising (i) at least one metal chosen from nickel and cobalt andoptionally (ii) at least one metal chosen from manganese, lithium andaluminum; and a liquid comprising lithium sulfate;

separating the liquid and the solid from one another to obtain the metalhydroxide;

submitting the liquid comprising lithium sulfate to an electromembraneprocess for converting the lithium sulfate into hydroxide; and

reusing at least first portion of the lithium hydroxide obtained by theelectromembrane process for reacting with the metal sulfate;

reacting at least a second portion of the lithium hydroxide obtained bythe electromembrane process with the obtained metal hydroxide to obtaina mixture of metal hydroxides; and

roasting the mixture of metal hydroxides to obtain the metal oxide.

According to another aspect of the present disclosure, there is provideda process for preparing a metal hydroxide comprising at least one metalchosen from nickel, cobalt, manganese, lithium and aluminum, the processcomprising:

reacting a metal sulfate comprising at least one metal chosen fromnickel, cobalt, manganese, lithium and aluminum with a base andoptionally a chelating agent in order to obtain a solid comprising themetal hydroxide and a liquid comprising lithium sulfate;

separating the liquid and the solid from one another to obtain the metalhydroxide;

submitting the liquid comprising lithium sulfate to an electromembraneprocess for converting the lithium sulfate into lithium hydroxide; and

reusing the lithium hydroxide obtained by the electromembrane processfor reacting with the metal sulfate.

According to another aspect, there is provided a process for preparing ametal oxide comprising at least one metal chosen from nickel, cobalt,manganese, lithium and aluminum, the process comprising:

reacting a metal sulfate comprising at least one metal chosen fromnickel, cobalt, manganese, lithium and aluminum with a base andoptionally a chelating agent to obtain a solid comprising a metalhydroxide at least one metal chosen from nickel, cobalt, manganese,lithium and aluminum, and a liquid comprising lithium sulfate;

separating the liquid and the solid from one another to obtain the metalhydroxide;

submitting the liquid comprising lithium sulfate to an electromembraneprocess for converting the lithium sulfate into lith ium hydroxide; and

reusing at least a first portion of the lithium hydroxide obtained bythe electromembrane process for reacting with the metal sulfate;

reacting at least a second portion of the lithium hydroxide obtained bythe electromembrane process with the obtained metal hydroxide to obtaina mixture of metal hydroxides; and

roasting the mixture of metal hydroxides to obtain the metal oxide.

According to an aspect of the present disclosure, there is provided aprocess for preparing a metal hydroxide comprising (i) at least onemetal chosen from nickel and cobalt and optionally (ii) at least onemetal chosen from manganese, lithium and aluminum, the processcomposing:

reacting a metal sulfate and/or a metal nitrate comprising (i) at leastone metal chosen from nickel and cobalt and optionally (ii) at least onemetal chosen from manganese, lithium and aluminum with lithiumhydroxide, sodium hydroxide and/or potassium hydroxide and optionally achelating agent in order to obtain a solid comprising the metalhydroxide and a liquid comprising at least one of lithium sulfate,lithium nitrate, sodium sulfate, sodium nitrate, potassium sulfate,potassium nitrate;

separating the liquid and the solid from one another to obtain the metalhydroxide;

submitting the liquid comprising at least one of lithium sulfate,lithium nitrate, sodium sulfate, sodium nitrate, potassium sulfate andpotassium nitrate to an electromembrane process for converting the leastone of lithium sulfate, lithium nitrate, sodium sulfate sodium nitrate,potassium sulfate, potassium nitrate, into at least one of least one oflithium hydroxide, sodium hydroxide, potassium hydroxide; and

reusing the at least one of lithium hydroxide, sodium hydroxide andpotassium hydroxide obtained by the electromembrane process for reactingwith the metal sulfate and/or metal nitrate.

According to another aspect, there is provided a process for preparing ametal oxide comprising (i) at least one metal chosen from nickel andcobalt and optionally (ii) at least one metal chosen from manganese,lithium and aluminum, the process comprising:

reacting a metal sulfate and/or a metal nitrate comprising (i) at leastone metal chosen from nickel and cobalt and optionally (ii) at least onemetal chosen from manganese, lithium and aluminum with lithiumhydroxide, sodium hydroxide and/or potassium hydroxide and optionally achelating agent to obtain a solid comprising a metal hydroxidecomprising (i) at least one metal chosen from nickel and cobalt andoptionally (ii) at least one metal chosen from manganese, lithium andaluminum, and a liquid comprising at least one of lithium sulfate,lithium nitrate, sodium sulfate, sodium nitrate, potassium sulfate andpotassium nitrate;

separating the liquid and the solid from one another to obtain the metalhydroxide;

submitting the liquid comprising at least one of lithium sulfate,lithium nitrate, sodium sulfate, sodium nitrate, potassium sulfate and,potassium nitrate to an electromembrane process for converting the atleast one of lithium sulfate, lithium nitrate, sodium sulfate, sodiumnitrate, potassium sulfate and potassium nitrate into at least one ofleast one of lithium hydroxide, sodium hydroxide and potassiumhydroxide; and

reusing at least a first portion of the at least one, of lithiumhydroxide, sodium hydroxide and potassium hydroxide obtained by theelectromembrane process for reacting with the metal sulfate and/or themetal nitrate;

reacting at least a second portion of the at least one of lithiumhydroxide, sodium hydroxide and potassium hydroxide obtained by theelectromembrane process with the obtained metal hydroxide to obtain amixture of metal hydroxides; and

roasting the mixture of metal hydroxides to obtain the metal oxide.

According to another aspect of the present disclosure, there is provideda process for preparing a metal hydroxide comprising at least, one metalchosen from nickel, cobalt, manganese, lithium and aluminum, the processcomprising.

reacting a metal sulfate and/or a metal nitrate comprising at least onemetal chosen from nickel, cobalt, manganese, lithium and aluminum with abase and optionally a chelating agent in order to obtain a solidcomprising the metal hydroxide and a liquid comprising at least one oflithium sulfate, lithium nitrate, sodium sulfate, sodium nitrate,potassium sulfate and potassium nitrate;

separating the liquid and the solid from one another to obtain the metalhydroxide;

submitting the liquid comprising at least one of lithium sulfate,lithium nitrate, sodium sulfate, sodium nitrate, potassium sulfate andpotassium nitrate to an electromembrane process for converting the leastone of lithium sulfate, lithium nitrate, sodium sulfate, sodium nitrate,potassium sulfate and potassium nitrate into at least one of lithiumhydroxide, sodium hydroxide and potassium hydroxide; and

reusing the at least one of lithium hydroxide, sodium hydroxide andpotassium hydroxide obtained by the electromembrane process for reactingwith the metal sulfate and/or the metal nitrate.

According to another aspect, there is provided a process for preparing,a metal oxide comprising at least one metal chosen from nickel, cobalt,manganese, lithium and aluminum, the process comprising:

reacting a metal sulfate and/or a metal nitrate comprising at least onemetal chosen from nickel, cobalt, manganese, lithium and aluminum with abase and optionally a chelating agent to obtain a solid comprising ametal hydroxide comprising at least one metal chosen from nickel,cobalt, manganese, lithium and aluminum, and a liquid comprising atleast one of lithium sulfate, lithium nitrate, sodium sulfate, sodiumnitrate, potassium sulfate and potassium nitrate;

separating the liquid and the solid from one another to obtain the metalhydroxide;

submitting the liquid comprising the at least one of lithium sulfate,lithium nitrate, sodium sulfate, sodium nitrate, potassium sulfate andpotassium nitrate to an electromembrane process for converting the atleast one of lithium sulfate, lithium nitrate, sodium sulfate, sodiumnitrate, potassium sulfate and potassium nitrate into at least one oflithium hydroxide, sodium hydroxide and potassium hydroxide; and

reusing at least a first portion of the at least one of lithiumhydroxide, sodium hydroxide and potassium hydroxide obtained by theelectromembrane process for reacting with the metal sulfate and/or metalnitrate;

reacting at least a second portion of the at least one of lithiumhydroxide, sodium hydroxide and potassium hydroxide obtained by theelectromembrane process with the obtained metal hydroxide to obtain amixture of metal hydroxides; and

roasting the mixture of metal hydroxides to obtain the metal oxide.

According to another aspect of the present disclosure, there is provideda process for preparing a metal hydroxide comprising at least one metalchosen from nickel, cobalt, manganese, lithium and aluminum, the processcomprising:

reacting a first metal sulfate and/or a first metal nitrate comprisingat least one metal chosen from nickel, cobalt, manganese, lithium andaluminum with a base comprising a second metal and optionally achelating agent in order to obtain a solid comprising the metalhydroxide and a liquid comprising at least one of a second metal sulfateand a second metal nitrate;

separating the liquid and the solid from one another to obtain the metalhydroxide;

submitting the liquid comprising at least one of the second metalsulfate and the second metal nitrate to an electromembrane process forconverting at least one of the second metal sulfate and the second metalnitrate into a second metal hydroxide; and

reusing the second metal hydroxide obtained by the electromembraneprocess for reacting with the first metal sulfate and/or the first metalnitrate.

According to another aspect, there is provided a process for preparing ametal oxide comprising at least one metal chosen from nickel, cobalt,manganese, lithium and aluminum, the process comprising:

reacting a first metal sulfate and/or a first metal nitrate comprising,at least one metal chosen from nickel, cobalt, manganese, lithium andaluminum with a base comprising a second metal and optionally achelating agent to obtain a solid comprising a metal hydroxidecomprising at least one metal chosen from nickel, cobalt, manganese,lithium and aluminum, and a liquid comprising at least one of a secondmetal sulfate and a second metal nitrate;

separating the liquid and the solid from one another to obtain the metalhydroxide;

submitting the liquid comprising the at least one of a second metalsulfate, and a second metal nitrate to an electromembrane process forconverting the at least one of a second metal sulfate and a second metalnitrate into a second metal hydroxide; and

reusing at least a first portion of the second metal hydroxide obtainedby the electromembrane process for reacting with the first metal sulfateand/or the first metal nitrate;

reacting at least a second portion of the second metal hydroxideobtained by the electromembrane process with the obtained metalhydroxide to obtain a mixture of metal hydroxides; and

roasting, the mixture of metal hydroxides to obtain the metal oxide.

According to another aspect, there is provided a process for preparing ametal hydroxide comprising (i) at least one metal chosen from nickel andcobalt and optionally (ii) at least one metal chosen from manganese,lithium and aluminum, the process comprising:

reacting a metal sulfate and/or a metal nitrate comprising (i) at leastone metal chosen from nickel and cobalt and optionally (ii) at least onemetal chosen from manganese, lithium and aluminum with lithiumhydroxide, sodium hydroxide and/or potassium hydroxide and optionally achelating agent in order to obtain a solid comprising the metalhydroxide and a liquid comprising at least one of lithium sulfate,lithium nitrate, sodium sulfate, sodium nitrate, potassium sulfate andpotassium nitrate;

separating the liquid and the solid from one another to obtain the metalhydroxide;

submitting the liquid comprising at least one of lithium sulfate,lithium nitrate, sodium sulfate, sodium nitrate to an electromembraneprocess for converting the least one of lithium sulfate, lithiumnitrate, sodium sulfate, sodium nitrate, potassium sulfate and potassiumnitrate into at least one of ieast one of lithium hydroxide, sodiumhydroxide and potassium hydroxide; and

reusing the at least one of lithium hydroxide, sodium hydroxide andpotassium hydroxide obtained by the electromembrane process for reactingwith the metal sulfate and/or metal nitrate.

According to another aspect there is provided a process for preparing ametal hydroxide comprising (i) at least one metal chosen from nickel andcobalt and optionally (ii) at least one metal chosen from manganese,lithium and aluminum, the process comprising:

reacting a metal sulfate comprising (i) at least one metal chosen fromnickel and cobalt and optionally (ii) at least one metal chosen frommanganese, lithium and aluminum with lithium hydroxide, sodium hydroxideand/or potassium hydroxide and optionally a chelating agent in order toobtain a solid comprising the metal hydroxide and a liquid comprising atleast one of lithium sulfate, sodium sulfate and potassium sulfate;

separating the liquid and the solid from one another to obtain the metalhydroxide;

submitting the liquid comprising at least one of lithium sulfate, sodiumsulfate and potassium sulfate to an electromembrane process forconverting the least one of lithium sulfate, sodium sulfate andpotassium sulfate into at least one of least one of lithium hydroxide,sodium hydroxide and potassium hydroxide; and

reusing the at least one of lithium hydroxide, sodium hydroxide andpotassium hydroxide obtained by the electromembrane process for reactingwith the metal sulfate.

According to another aspect there is provided a process a process forpreparing a metal hydroxide comprising at least one metal chosen fromnickel, cobalt, manganese, lithium and aluminum, the process comprising:

reacting a metal sulfate and/or a metal nitrate comprising at least onemetal chosen from nickel, cobalt, manganese, lithium and aluminum with abase chosen from LiOH, NaOH, KOH, RbOH, CsOH, Mg(OH)₂, Ca(OH)₂, Sr(OH)₂,or Ba(OH)₂ and optionally a chelating agent in order to obtain a solidcomprising the metal hydroxide and a liquid comprising at least one ofLi₂SO₄ Na₂SO₄, K₂SO₄, Rb₂SO₄, Cs₂SO₄, MgSO₄, CaSO₄, SrSO₄, BaSO₄, LiNO₃NaNO₃, KNO₃, RbNO₃, CsNO₃, Mg(NO₃)₂, Ca(NO₃)₂, Sr(NO₃)₂ and Ba(NO₃)₂,

separating the liquid and the solid from one another to obtain the metalhydroxide;

submitting the liquid comprising at least one of Li₂SO₄ Na₂SO₄, K₂SO₄,Rb₂SO₄, Cs₂SO₄, MgSO₄, CaSO₄, SrSO₄, BaSO₄, LiNO₃ NaNO₃, KNO₃, RbNO₃,CsNO₃, Mg(NO₃)₂, Ca(NO₃)₂, Sr(NO₃)₂ and Ba(NO₃)₂ to an electromembraneprocess for converting the least one of Li₂SO₄ Na₂SO₄, K₂SO₄, Rb₂SO₄,Cs₂SO₄, MgSO₄, CaSO₄, SrSO₄, BaSO₄, LiNO₃ NaNO₃, KNO₃, RbNO₃, CsNO₃,Mg(NO₃)₂, Ca(NO₃)₂, Sr(NO₃)₂ and Ba(NO₃)₂ into at least one of LiOH,NaOH, KOH, RbOH, CsOH, Mg(OH)₂, Ca(OH)₂, Sr(OH)₂, and Ba(OH)₂; and

reusing the at least one of LiOH, NaOH, KOH, RbOH, CsOH, Mg(OH)₂,Ca(OH)₂, Sr(OH)₂, and Ba(OH)₂ obtained by the electromembrane processfor reacting with the metal sulfate and/or the metal nitrate.

According to mother aspect, there is provided a process for preparing ametal oxide comprising (i) at least one metal chosen from nickel andcobalt and optionally (ii) at least one metal chosen from manganese,lithium and aluminum, said process comprising:

reacting a metal sulfate and/or a metal nitrate comprising at east onemetal chosen from nickel, cobalt, manganese, lithium and aluminum with abase chosen from LiOH, NaOH, KOH, RbOH, CsOH, Mg(OH)₂, Ca(OH)₂, Sr(OH)₂,or Ba(OH)₂ and optionally a chelating agent in order to obtain a solidcomprising the metal hydroxide and a liquid comprising at least one ofLi₂SO₄ Na₂SO₄, K₂SO₄, Rb₂SO₄, Cs₂SO₄, MgSO₄, CaSO₄, SrSO₄, BaSO₄, LiNO₃NaNO₃, KNO₃, RbNO₃, CsNO₃, Mg(NO₃)₂, Ca(NO₃)₂, Sr(NO₃)₂, and Ba(NO₃)₂,

separating said liquid and said solid from one another to obtain saidmetal hydroxide;

submitting said liquid comprising at least one of Li₂SO₄ Na₂SO₄, K₂SO₄,Rb₂SO₄, Cs₂SO₄, MgSO₄, CaSO₄, SrSO₄, BaSO₄, LiNO₃ NaNO₃, KNO₃, RbNO₃,CsNO₃, Mg(NO₃)₂, Ca(NO₃)₂, Sr(NO₃)₂ and Ba(NO₃)₂ to an electromembraneprocess for converting at least one of Li₂SO₄ Na₂SO₄, K₂SO₄, Rb₂SO₄,Cs₂SO₄, MgSO₄, CaSO₄, SrSO₄, BaSO₄, LiNO₃ NaNO₃, KNO₃, RbNO₃, CsNO₃,Mg(NO₃)₂, Ca(NO₃)₂, Sr(NO₃)₂ and Ba(NO₃)₂ into at least one of LiOH,NaOH. KOH, RbOH, CsOH, Mg(H)₂, Ca(OH)₂, Sr(OH)₂, or Ba(OH)₂; and

reusing at least a first portion of said at least one of LiOH, NaOH,KOH, RbOH, CsOH, Mg(OH)₂, Ca(OH)₂, Sr(OH)₂, or Ba(OH)₂ obtained by saidelectromembrane process for reacting with said metal sulfate;

reacting at least a second portion of said at least one of LiOH, NaOH.KOH, RbOH, CsOH, Mg(OH)₂, Ca(OH)₂, Sr(OH)₂, or Ba(OH)₂ obtained by saidelectromembrane process with said obtained metal hydroxide to obtain amixture of metal hydroxides; and

roasting said mixture of metal hydroxides to obtain said metal oxide.

According to an aspect of the present disclosure, there is provided aprocess for preparing a metal carbonate comprising (i) at least onemetal chosen from nickel and cobalt and optionally (ii) at least onemetal chosen from manganese, lithium and aluminum, the processcomprising.

reacting a metal sulfate and/or a metal nitrate comprising (i) at leastone metal chosen from nickel and cobalt and optionally (ii) at least onemetal chosen from manganese, lithium and aluminum with lithiumcarbonate, sodium carbonate and/or potassium carbonate and optionally achelating agent in order to obtain a solid comprising the metalcarbonate and a liquid comprising at least one of lithium sulfate,lithium nitrate, sodium sulfate, sodium nitrate, potassium sulfate,potassium nitrate;

separating the liquid and the solid from one another to obtain the metalcarbonate;

submitting the liquid comprising at least one of lithium sulfate,lithium nitrate, sodium sulfate, sodium nitrate, potassium sulfate andpotassium nitrate to an electromembrane process for converting the leastone of lithium sulfate, lithium nitrate, sodium sulfate, sodium nitrate,potassium sulfate, potassium nitrate, into at least one of least one oflithium hydroxide, sodium hydroxide and potassium hydroxide;

converting the at least one of least one of lithium hydroxide, sodiumhydroxide, potassium hydroxide into at least one of at least one ofleast one of lithium carbonate, sodium carbonate and potassium hydroxideby a carbonatation process; and

reusing the at least one of lithium carbonate, sodium carbonate andpotassium hydroxide obtained by the carbonatation process for reactingwith the metal sulfate and/or metal nitrate.

According to another aspect, there is provided a process for preparing ametal oxide comprising (i) at least one metal chosen from nickel andcobalt and optionally (ii) at least one metal chosen from manganese,lithium and aluminum, the process comprising:

reacting a metal sulfate and/or a metal nitrate comprising (i) at leastone metal chosen from nickel and cobalt and optionally (ii) at least onemetal chosen from manganese, lithium and aluminum with lithiumcarbonate, sodium carbonate and/or potassium carbonate and optionally achelating agent to obtain a solid comprising a metal carbonatecomprising (i) at least one metal chosen from nickel and cobalt andoptionally (ii) at least one metal chosen from manganese, lithium andaluminum, and a liquid comprising at least one of lithium sulfate,lithium nitrate, sodium sulfate, sodium nitrate, potassium sulfate andpotassium nitrate;

separating the liquid and the solid from one another to obtain the metalcarbonate;

submitting the liquid comprising at least one of lithium sulfate,lithium nitrate, sodium sulfate, sodium nitrate, potassium sulfate andpotassium nitrate to an electromembrane process for converting the atleast one of lithium sulfate, lithium nitrate, sodium sulfate, sodiumnitrate, potassium sulfate and potassium nitrate into at least one ofleast one of lithium hydroxide, sodium hydroxide and potassiumhydroxide; and

converting the at least one of least one of lithium hydroxide, sodiumhydroxide, potassium hydroxide into at least one of at least one ofleast one of lithium carbonate, sodium carbonate and potassium carbonateby a carbonatation process; and

reusing at least a first portion of the at least one of lithiumcarbonate, sodium carbonate and potassium carbonate obtained by thecarbonatation process for reacting with the metal sulfate and/or themetal nitrate;

reacting at least a second portion of the at least one of lithiumcarbonate, sodium carbonate and potassium carbonate obtained by thecarbonatation process with the obtained metal carbonate to obtain amixture of metal carbonates; and

roasting the mixture a carbonates to obtain the metal oxide.

According to another aspect of the present disclosure, there is provideda process for preparing a metal carbonate comprising at least one metalchosen from nickel, cobalt, manganese, lithium and aluminum, the processcomprising:

reacting a first metal sulfate and/or a first metal nitrate comprisingat least one metal chosen from nickel, cobalt, manganese, lithium andaluminum with a base comprising a second metal and optionally achelating agent in order to obtain a solid comprising the metalcarbonate and a liquid comprising at least one of a second metal sulfateand a second metal nitrate;

separating the liquid and the solid from one another to obtain the metalcarbonate;

submitting the liquid comprising at least one of the second r metalsulfate and the second metal nitrate to an electromembrane process forconverting at least one of the second metal sulfate and the second metalnitrate into a second metal hydroxide;

converting the second metal hydroxide into a second metal carbonate thatis at least one lithium carbonate, sodium carbonate and potassiumcarbonate by a carbonatation process; and

reusing the second metal carbonate obtained by the carbonatation processfor reacting with the first metal sulfate and/or the first metalnitrate.

According to another aspect, there is provided a process for preparing ametal oxide composing at least one metal chosen from nickel, cobalt,manganese, lithium and aluminum, the process comprising:

reacting a first metal sulfate and/or a first metal nitrate comprisingat least one metal chosen from nickel, cobalt, manganese, lithium andaluminum with a base comprising a second metal and optionally achelating agent to obtain a solid comprising a metal carbonatecomprising at least one metal chosen from nickel, cobalt, manganese,lithium and aluminum, and a liquid composing at least one of a secondmetal sulfate and a second metal nitrate;

separating the liquid and the solid from one another to obtain the metalcarbonate;

submitting the liquid comprising the at least one of a second metalsulfate and a second metal nitrate to an electromembrane process forconverting the at least one of a second metal sulfate and a second metalnitrate into a second metal hydroxide;

converting the second metal hydroxide into a second metal carbonate thatis at feast one of lithium carbonate, sodium carbonate and potassiumcarbonate by a carbonatation process; and

reusing at least a first portion of the second metal carbonate obtainedby the carbonatation process for reacting with the first metal sulfateand/or the first metal nitrate;

reacting at least a second portion of the second metal carbonateobtained by the carbonatation process with the obtained metal hydroxideto obtain a mixture of metal carbonates; and

roasting the mixture of metal carbonates to obtain the metal oxide.

According to another aspect, there is provided a process for preparing ametal hydroxide comprising (i) at least one metal chosen from nickel andcobalt and optionally (ii) at least one metal chosen from manganese,lithium and aluminum, said process comprising.

reacting a metal sulfate comprising (i) lithium; (ii) at least one metalchosen from nickel and cobalt and optionally (iii) at least one metalchosen from manganese and aluminum with sodium hydroxide and optionallya chelating agent in order to obtain a solid comprising said metalhydroxide and a liquid composing sodium sulfate and lithium sulfate;

separating said liquid and said solid from one another to obtain saidmetal hydroxide;

submitting said liquid comprising sodium sulfate and lithium sulfate toan electromembrane process for converting said sodium sulfate and saidlithium sulfate into sodium hydroxide and lithium hydroxide; and

reusing said sodium hydroxide obtained by said electromembrane processfor reacting with said metal sulfate.

According to another aspect, there is provided a process for preparing ametal hydroxide comprising (i) at least one metal chosen from nickel andcobalt and optionally (ii) at least one metal chosen from manganese,lithium and aluminum, said process composing:

reacting a metal sulfate comprising (i) lithium; (ii) at least one metalchosen from nickel and cobalt and optionally (iii) at least one metalchosen from manganese and aluminum with sodium hydroxide and optionallya chelating agent in order to obtain a solid composing said metalhydroxide and a liquid comprising sodium sulfate and lithium sulfate;

separating said liquid and said solid from one another to obtain saidmetal hydroxide;

separating sodium sulfate and lithium sulfate from one another;

submitting said liquid comprising sodium sulfate to an electromembraneprocess for converting said sodium sulfate into sodium hydroxide; and

reusing said sodium hydroxide obtained by said electromembrane processfor reacting with said metal sulfate.

According to another aspect, there is provided a process for preparing ametal hydroxide comprising (i) at least one metal chosen from nickel andcobalt and optionally iii) at least one metal chosen from manganese,lithium and aluminum, said process comprising:

reacting a metal sulfate comprising (i) at least one metal chosen fromnickel and cobalt and optionally (ii) at least one metal chosen frommanganese, lithium and aluminum with sodium hydroxide and optionally achelating agent, in order to obtain a solid comprising said metalhydroxide and a liquid comprising sodium sulfate:

separating said liquid and said solid from one another to obtain saidmetal hydroxide;

submitting said liquid comprising sodium sulfate to an electromembraneprocess for converting said sodium sulfate into sodium hydroxide; and

reusing said sodium hydroxide obtained by said electromembrane processfor reacting with said metal sulfate.

According to another aspect there is provided a process a process forpreparing a metal carbonate comprising at least one metal chosen fromnickel, cobalt, manganese, lithium and aluminum, the process comprising.

reacting a metal sulfate and/or a metal nitrate comprising at least onemetal chosen from nickel, cobalt, manganese, lithium and aluminum with abase chosen from Li₂CO₃, Na₂CO₃, K₂CO₃, Rb₂CO₃, Cs₂CO₃, MgCO₃, CaCO₃,SrCO₃ and BaCO₃ and optionally a chelating agent in order to obtain asolid comprising the metal carbonate and a liquid comprising at leastone of Li₂SO₄ Na₂SO₄, K₂SO₄, Rb₂SO₄, Cs₂SO₄, MgSO₄, CaSO₄, SrSO₄, BaSO₄,LiNO₃ NaNO₃, KNO₃, RbNO₃, CsNO₃, Mg(NO₃)₂, Ca(NO₃)₂, Sr(NO₃)₂ andBa(NO₃)₂,

separating the liquid and the solid from one another to obtain the metalhydroxide;

submitting the liquid comprising at least one of Li₂SO₄ Na₂SO₄, K₂SO₄,Rb₂SO₄, Cs₂SO₄, MgSO₄, CaSO₄, SrSO₄, BaSO₄, LiNO₃ NaNO₃, KNO₃, RbNO₃,CsNO₃, Mg(NO₃)₂, Ca(NO₃)₂, Sr(NO₃)₂ and Ba(NO₃)₂ to an electromembraneprocess for converting the least one of Li₂SO₄ Na₂SO₄, K₂SO₄, Rb₂SO₄,Cs₂SO₄, MgSO₄, CaSO₄, SrSO₄, BaSO₄, LiNO₃ NaNO₃, KNO₃, RbNO₃, CsNO₃,Mg(NO₃)₂, Ca(NO₃)₂, Sr(NO₃)₂ and Ba(NO₃)₂ into at least one of LiOH,NaOH, KOH, RbOH, CsOH, Mg(OH)₂, Ca(OH)₂, Sr(OH)₂, and Ba(OH)₂;

converting the at least one of LiOH, NaOH, KOH, RbOH, CsOH, Mg(OH)₂,Ca(OH)₂, Sn(OH)₂, and Ba(OH)₂ into Li₂CO₃, Na₂CO₃, K₂CO₃, Rb₂CO₃,Cs₂CO₃, MgCO₃, CaCO₃, SrCO₃ and BaCO₃ by a carbonatation process; and

reusing the at least one of Li₂CO₃, Na₂CO₃, K₂CO₃, Rb₂CO₃, Cs₂CO₃,MgCO₃, CaCO₃, SrCO₃ and BaCO₃ obtained by the carbonation process forreacting with the metal sulfate and/or the metal nitrate.

According to another aspect, there is provided a process for preparing ametal oxide comprising (i) at least one metal chosen from nickel andcobalt and optionally (ii) at least one metal chosen from manganese,lithium and aluminum, said process comprising:

reading a metal sulfate and/or a metal nitrate comprising at least onemetal chosen from nickel, cobalt, manganese, lithium and aluminum with abase chosen from Li₂CO₃, Na₂CO₃, K₂CO₃, Rb₂CO₃, Cs₂CO₃, MgCO₃, CaCO₃,SrCO₃ and BaCO₃ and optionally a chelating agent in order to obtain asolid comprising the metal carbonate and a liquid comprising at leastone of Li₂SO₄ Na₂SO₄, K₂SO₄, Rb₂SO₄, Cs₂SO₄, MgSO₄, CaSO₄, SrSO₄, BaSO₄,LiNO₃ NaNO₃, KNO₃, RbNO₃, CsNO₃, Mg(NO₃)₂, Ca(NO₃)₂, Sr(NO₃)₂ andBa(NO₃)₂,

-   -   separating said liquid and said solid from one another to obtain        said metal carbonate;

submitting said liquid comprising at least one of Li₂SO₄ Na₂SO₄, K₂SO₄,Rb₂SO₄, Cs₂SO₄, MgSO₄, CaSO₄, SrSO₄, BaSO₄, LiNO₃ NaNO₃, KNO₃, RbNO₃,CsNO₃, Mg(NO₃)₂, Ca(NO₃)₂, Sr(NO₃)₂ and Ba(NO₃)₂ to an electromembraneprocess for converting at least one of Li₂SO₄ Na₂SO₄, K₂SO₄, Rb₂SO₄,Cs₂SO₄, MgSO₄, CaSO₄, SrSO₄, BaSO₄, LiNO₃ NaNO₃, KNO₃, RbNO₃, CsNO₃,Mg(NO₃)₂, Ca(NO₃)₂, Sr(NO₃)₂ and Ba(NO₃)₂ into at least one of LiOH,NaOH, KOH, RbOH, CsOH, Mg(OH)₂, Ca(OH)₂, Sr(OH)₂, or Ba(OH)₂;

converting the at least one of LiOH, NaOH, KOH, RbOH, CsOH, Mg(OH)₂,Ca(OH)₂, Sr(OH)₂, and Ba(OH)₂ into Li₂CO₃, Na₂CO₃, K₂CO₃, Rb₂CO₃,Cs₂CO₃, MgCO₃, CaCO₃, SrCO₃ and BaCO₃ by a carbonatation process; and

reusing at least a first portion of said at least one of Li₂CO₃, Na₂CO₃,K₂CO₃, Rb₂CO₃, Cs₂CO₃, MgCO₃, CaCO₃, SrCO₃ and BaCO₃ obtained by saidcarbonatation process for reacting with said metal sulfate;

reacting at least a second portion of said at least one of Li₂CO₃,Na₂CO₃, K₂CO₃, Rb₂CO₃, Cs₂CO₃, MgCO₃, CaCO₃, SrCO₃ and BaCO₃ obtained bysaid carbonatation process with said obtained metal carbonate to obtaina mixture of metal carbonates; and

roasting said mixture of metal carbonates to obtain said metal oxide.

According to another aspect, there is provided a process for preparing ametal oxide comprising (i) at least one metal chosen from nickel andcobalt and optionally (ii) at least one metal chosen from manganese,lithium and aluminum, said process comprising:

reacting a metal sulfate comprising (i) lithium, (ii) at least one metalchosen from nickel and cobalt and optionally (iii) at least one metalchosen from manganese and aluminum with sodium hydroxide and optionallya chelating agent in order to obtain a solid composing said metalhydroxide and a liquid comprising sodium sulfate and lithium sulfate;

separating said liquid and said solid from one another to obtain saidmetal hydroxide;

submitting said liquid comprising sodium sulfate and lithium sulfate toan electromembrane process for converting said sodium sulfate and saidlithium sulfate into sodium hydroxide and lithium hydroxide;

separating said lithium hydroxide and said sodium hydroxide from oneanother;

reusing at least a first portion of said sodium hydroxide obtained bysaid electromembrane process for reacting with said metal sulfate;

reacting at least a first portion of said lithium hydroxide obtained bysaid electromembrane process with said, obtained metal hydroxide toobtain a mixture of metal hydroxides; and

roasting said mixture of metal hydroxides to obtain said metal oxide.

According to another aspect, there is provided a process for preparing ametal oxide comprising at least one metal chosen from nickel, cobalt,manganese, lithium and aluminum, the process comprising:

reacting a first metal sulfate and/or a first metal nitrate comprisingat least one metal chosen from nickel, cobalt, manganese, lithium andaluminum with a base comprising a second metal and optionally achelating agent to obtain a solid comprising a metal hydroxidecomprising at least one metal chosen from nickel, cobalt, manganese,lithium and aluminum, and a liquid comprising at least one of a secondmetal sulfate and a second metal nitrate;

separating the liquid and the solid from one another to obtain the metalhydroxide;

submitting the liquid comprising the at least one of a second metalsulfate and a second metal nitrate to an electromembrane process forconverting the at least one of a second metal sulfate and a second metalnitrate into a second metal hydroxide; and

reusing at least a first portion of the second metal hydroxide obtainedby the electromembrane process for reacting with the first metal sulfateand/or the first metal nitrate;

mixing a third metal hydroxide with the obtained metal hydroxide toobtain a mixture of metal hydroxides; and

roasting the mixture of metal hydroxides to obtain the metal oxide.

According to another aspect of the present disclosure, there is provideda process for preparing a metal hydroxide comprising (i) at least onemetal chosen from nickel and cobalt and optionally (ii) at least onemetal chosen from manganese, lithium and aluminum, the processcomprising:

reacting a metal sulfate comprising (i) at least one metal chosen fromnickel and cobalt and optionally (ii) at least one metal chosen frommanganese, lithium and aluminum with sodium hydroxide and optionally achelating agent in order to obtain a solid comprising the metalhydroxide and a liquid comprising sodium sulfate;

separating the liquid and the solid from one another to obtain the metalhydroxide;

submitting the liquid comprising sodium sulfate to an electromembraneprocess for converting the sodium sulfate into sodium hydroxide; and

reusing the sodium hydroxide obtained by the electromembrane process forreacting with the metal sulfate.

According to another aspect, there is provided a process for preparing ametal oxide comprising (i) at least one metal chosen from nickel andcobalt and optionally (ii) at least one metal chosen from manganese,lithium and aluminum, the process comprising:

reacting a metal sulfate comprising (i) at least one metal chosen fromnickel and cobalt and optionally (ii) at least one metal chosen frommanganese, lithium and aluminum with, sodium hydroxide and optionally achelating agent to obtain a solid comprising a metal hydroxidecomprising (i) at least one metal chosen from nickel and cobalt andoptionally (ii) at least one metal chosen from manganese, lithium andaluminum, and a liquid comprising lithium sulfate;

separating the liquid and the solid from one another to obtain the metalhydroxide;

submitting the liquid comprising sodium sulfate to an electromembraneprocess for converting the sodium sulfate into sodium hydroxide; and

reusing at least a first portion of the sodium hydroxide obtained by theelectromembrane process for reacting with the metal sulfate;

mixing another metal hydroxide with e obtained metal hydroxide to obtaina mixture of metal hydroxides; and

roasting the mixture of metal hydroxides to obtain the metal oxide.

According to another aspect, there is provided a process for preparing ametal hydroxide comprising (i) at least one metal chosen from nickel andcobalt and optionally (ii) at least one metal chosen from manganese,lithium and aluminum, said process comprising.

reacting a metal sulfate comprising (i) at least one metal chosen fromnickel and cobalt and optionally (iii) at least one metal chosen frommanganese and aluminum with sodium hydroxide and optionally a chelatingagent in order to obtain a solid comprising said metal hydroxide and aliquid comprising sodium sulfate and optionally lithium sulfate;

separating said liquid and said solid from one another to obtain saidmetal hydroxide;

submitting said liquid comprising sodium sulfate and optionally lithiumsulfate to an electromembrane process for converting said sodium sulfateand optionally said lithium sulfate into sodium hydroxide and optionallylithium hydroxide; and

reusing said sodium hydroxide obtained by said electromembrane processfor reacting with said metal sulfate.

According to another aspect, there is provided a process for preparing ametal hydroxide comprising (i) at least one metal chosen from nickel andcobalt and optionally (ii) at least one metal chosen from manganese,lithium and aluminum, the process comprising:

reacting a metal sulfate comprising (i) at least one metal chosen fromnickel and cobalt and optionally (ii) at least one metal chosen frommanganese, lithium and aluminum with lithium hydroxide, sodium hydroxideand/or potassium hydroxide and optionally a chelating agent in order toobtain a solid comprising the metal hydroxide and a liquid comprisinglithium sulfate, sodium sulfate and/or potassium sulfate;

separating the liquid and the did from one another to obtain the metalhydroxide;

submitting the liquid comprising lithium sulfate sodium sulfate and/orpotassium sulfate to an electromembrane process for converting thelithium sulfate, sodium sulfate and/or potassium sulfate into lithiumhydroxide, sodium hydroxide and/or potassium hydroxide respectively;

reusing the sodium hydroxide obtained by the electromembrane press forreacting with the metal sulfate; and

reusing the lithium hydroxide obtained by the electromembrane processfor reacting with the metal sulfate and/or with the metal hydroxide.

According to another aspect, there is provided the use of the metalhydroxide, the metal carbonate and/or the metal oxide obtained from aprocess described in the present disclosure in the manufacture of acathode.

According to another aspect, there is provided a method of using themetal hydroxide, the metal carbonate and/or the metal oxide obtainedfrom a process described in the present disclosure, the methodcomprising incorporating the metal hydroxide, the metal carbonate and/orthe metal oxide in the manufacture of a cathode.

BRIEF DESCRIPTION OF DRAWINGS

In the following drawings, which represent by way of example only,various embodiments of the disclosure:

FIG. 1 is a schematic diagram of a process according to an embodiment ofpresent disclosure;

FIG. 2 is a X-Ray diffraction pattern of cobalt hydroxide Co(OH)₂ (inblack) obtained using LiOH as base source and the theoreticaldiffraction peaks of this compound (vertical bars);

FIG. 3 is X-Ray, diffraction pattern of cobalt hydroxide Co(OH)₂ (inblack) obtained using NaOH as base source and the theoreticaldiffraction peaks of this compound (vertical bars);

FIG. 4 is a X-Ray diffraction pattern of LiCoO₂ (in black) obtained byusing the Co(OH)2 of FIG. 2 (in black) and the theoretical diffractionpeaks of this compound (vertical bars);

FIG. 5 is a X-Ray diffraction pattern of LiCoO₂ (in black) obtained byusing the Co(OH)2 of FIG. 3 and the theoretical diffraction peaks ofthis compound (vertical bars);

FIG. 6 represent charge/discharge curves of LiCoO₂;

FIG. 7 is a X-Ray diffraction pattern of Nickel-Cobalt-Aluminumhydroxide Ni_(0.8)Co_(0.15)Al_(0.05)O₂(OH)₂ (in black) and thetheoretical diffraction peaks of this compound (vertical bars);

FIG. 8 is a X-Ray diffraction pattern of the lithiatedNickel-Cobalt-Aluminum oxide LiNi_(0.8)Co_(0.15)Al_(0.05)O₂ (in black)and the theoretical diffraction peaks of this compound (vertical bars);

FIG. 9 is a charge/discharge curves of LiNi_(0.8)Co_(0.15)Al_(0.05)O₂;

FIG. 10 is a X-Ray diffraction pattern of Nickel-Manganese-Cobalthydroxide Ni_(0.8)Mn_(0.1)Co_(0.1)(OH)₂ (in black) and the theoreticaldiffraction peaks of this compound (vertical bars);

FIG. 11 is X-Ray diffraction pattern of lithiatedNickel-Manganese-Cobalt oxide LiNi_(0.8)Mn_(0.1)Co_(0.1)O₂ (in black)and the theoretical diffraction peaks of this compound (vertical bars);

FIG. 12 is a X-Ray diffraction pattern of Nickel-Manganese-Cobalthydroxide Ni_(0.6)Mn_(0.2)Co_(0.2)(OH)₂ (in black) and the theoreticaldiffraction peaks of this compound (vertical bars);

FIG. 13: X-Ray diffraction pattern of lithiated Nickel-Manganese-Cobaltoxide LiNi_(0.6)Mn_(0.2)Co_(0.2)O₂ (in black) and the theoreticaldiffraction peaks of this compound (vertical bars):

FIG. 14 represent charge/discharge curves ofLiNi_(0.6)Mn_(0.2)Co_(0.2)O₂;

FIG. 15 is a plot showing concentration of H₂SO₄ in the anolyte of atwo-compartment cell as a function of time in an example of electrolysisof Li₂SO₄;

FIG. 16 is a plot showing conductivity of anolyte and catholyte in atwo-compartment cell as a function of time in an example of electrolysisof Li₂SO₄:

FIG. 17 is a plot showing temperature of anolyte and catholyte atwo-compartment cell as a function of time in an example of electrolysisof Li₂SO₄;

FIG. 18 is a plot showing voltage in a two-compartment cell as afunction of time in an example of electrolysis of Li₂SO₄;

FIG. 19 is a plot showing flow rate of LiOH.H₂O as a function ofconcentration of H₂SO₄ in a two-compartment cell in an example ofelectrolysis of Li₂SO₄;

FIG. 20 is another plot showing flow rate of LiOH.H₂O as a function ofconcentration of H₂SO₄ in a two-compartment cell in an example ofelectrolysis of Li₂SO₄;

FIG. 21 is a plot showing current efficiency as a function ofconcentration of H₂SO₄ in a two-compartment cell in an example ofelectrolysis of Li₂SO₄;

FIG. 22 is a plot showing productivity of LiOH.H₂O as a function ofconcentration of H₂SO₄ in a two-compartment cell in an example, ofelectrolysis of Li₂SO₄;

FIG. 23 is a plot showing energy consumption as a function ofconcentration of H₂SO₄ in a two-compartment cell in an example ofelectrolysis of Li₂SO₄;

FIG. 24 is a schematic diagram of a process according to an embodimentof the present disclosure using LION as pH enhancer;

FIG. 25 is a schematic diagram of a process according to an embodimentof the present disclosure using NaOH as pH enhancer;

FIG. 26 is a schematic diagram of a process according to an, embodimentof the present disclosure using LiOH and/or NaOH as pH enhancer;

FIG. 27 is a schematic diagram of a process according to an embodimentof the present disclosure using NaOH as pH enhancer for a metalu sulfatesolution containing Lithium ions;

FIG. 28 is a schematic diagram of a process according to an embodimentof the present disclosure, with purification and/or concentration of thesulfate solution recovered before electromembrane process;

FIG. 29 is a schematic diagram of a process according to an embodimentof the present disclosure, with purification and/or concentration of thesulfate solution recovered before electromembrane process andconcentration of the anolyte solution and addition of H₂O₂;

FIG. 30 is a schematic diagram of a process according to an embodimentof the present disclosure for the core-shell synthesis using LiOH and/orNaOH as pH enhancer;

FIG. 31 is a schematic diagram of a process according to an embodimentof the present disclosure for the synthesis of a lithiated metal oxideusing Li2CO3 as pH enhancer for the precipitation of metal carbonate.

FIG. 32 is a schematic diagram of a process according to an embodimentof the present disclosure using nitric acid for the leaching of thetransition metal source.

FIG. 33 is a schematic diagram of a process for the production of highpurity sulfate salts using H₂SO₄ to leach the nickel cobalt concentrate;

FIG. 34 is a schematic diagram of a process for the production of highpurity sulfate salts; and

FIG. 35 is a schematic diagram of a process for the production of highpurity sulfate salts.

DETAILED DESCRIPTION OF VARIOUS EMBODIMENTS

Unless otherwise indicated, the definitions and embodiments described inthis and other sections are intended to be applicable to ail embodimentsand aspects of me present disclosure herein described for which they aresuitable as would be understood by a person skilled in the art.

As used in the present disclosure, the singular forms “a”, “an” and“the” include plural references unless the content dearly dictatesotherwise.

In understanding the scope of the present disclosure, the term“comprising” and its derivatives, as used herein, are intended to beopen ended terms that specify the presence of the stated features,elements, components, groups, integers, and/or steps, but do not excludethe presence of other unstated features, elements, components, groups,integers and/or steps. The foregoing also applies to words havingsimilar meanings such as the terms, “including”, “having” and theirderivatives. The term “consisting” and its derivatives, as used herein,are intended to be closed terms that specify the presence of the statedfeatures, elements, components, groups, integers, and/or steps, butexclude the presence of other unstated features, elements, components,groups, integers and/or steps. The term “consisting essentially of”, asused herein, is intended to specify the presence of the stated features,elements, components, groups, integers, and/or steps as well as thosethat do not materially affect the basic and novel characteristic(s) offeatures, elements, components, groups, integers, and/or steps.

Terms of degree such as “about” and “approximately” as used herein meana reasonable amount of deviation of the modified term such that the endresult is not significantly changed. These terms of degree should beconstrued as including a deviation of ±10% of the modified term if thisdeviation would not negate the meaning of the word it modifies.

The term “suitable” as used herein means that the selection of theparticular conditions would depend on the specific manipulation oroperation to be performed, but the selection would be well within theskill of a person trained in the art. All processes described herein areto be conducted under conditions sufficient to provide the desiredproduct. A person skilled, in the art would understand that all reactionconditions, including, when applicable, for example, reaction time,reaction temperature, reaction pressure, reactant ratio flow rate,reactant purity, current density, voltage, concentration, pH, oxidationreduction potential, cell area, type of membrane used, and recycle ratescan be varied to optimize the yield of the desired product and it iswithin their skill to do so.

The expression “is at least substantially maintained” as used hereinwhen referring to a value of a pH or a pH range that is maintainedduring a process of the disclosure or a portion thereof (for example,electrolysis, etc.) refers to maintaining the value of the pH or the pHrange at least 75, 80, 85, 90, 95, 96, 97, 98 or 99% of the time duringthe process or the portion thereof.

The expression “is at least substantially maintained” as used hereinwhen referring to a value of a concentration or a concentration rangethat is maintained during a process of the disclosure or a portionthereof (for example, electrolysis, etc.) refers to maintaining thevalue of the concentration or the concentration range at least 75, 80,85, 90, 95, 96, 97, 98 or 99% of the time during the process or theportion thereof.

The expression “is at least substantially maintained” as used hereinwhen referring to a value of a temperature or a temperature range thatis maintained during a process of the disclosure or a portion thereof(for example, electrolysis, etc.) refers to maintaining the value of thetemperature or the temperature range at least 75, 80, 85, 90, 95, 96,97, 98 or 99% of the time during the process or the portion thereof.

The expression “is at least substantially maintained” as used hereinwhen referring to a value of an electrical current density or anelectrical current density range that is maintained during a process ofthe disclosure or a portion thereof (for example, electrolysis, etc.)refers to maintaining the value of the electrical current density or theelectrical current density range at least 75, 80, 85, 90, 95, 96, 97, 98or 99% of the time during the process or the portion thereof.

The expression “is at least substantially maintained” as used hereinwhen referring to a value of an electrical current efficiency or anelectrical current efficiency range that is maintained during a processof the disclosure or a portion thereof (for example, electrolysis, etc.)refers to maintaining the value of the electrical current efficiency orthe electrical current efficiency range at least 75, 80, 85, 90, 95, 96,97, 98 or 99% of the time during the process or the portion thereof.

The expression “is at least substantially maintained” as used hereinwhen referring to a value of a voltage or a voltage range that ismaintained during a process of the disclosure or a portion thereof (forexample, electrolysis, etc.) refers to maintaining the value of thevoltage or the voltage range at least 75, 80, 85, 90, 95, 96, 97, 98 or99% of the time during the process or the portion thereof.

The term “electromembrane process” as used herein refers, for example toa process that uses ion-exchange membrane(s) and an electric potentialdifference as the driving force for ionic species. The electromembraneprocess can be, for example (a membrane) electrodialysis or (a membrane)electrolysis. For example, the electromembrane process can be a membraneelectrolysis.

The term “carbonatation process” as used herein refers, for example to aprocess in which a metal hydroxide will be converted into a metalcarbonate. For example, such a process can involve the use of gaseousCO₂. For example, such a process can involve bubbling of CO₂.

The below presented examples are non-limitative and are used to betterexemplify the processes of the present disclosure.

For example, the hydroxide can be chosen from nickel-cobalt-manganesehydroxides, nickel-cobalt-aluminum hydroxides, lithium-cobalthydroxides, nickel hydroxides, nickel-cobalt-manganese oxyhydroxides,nickel-cobalt-aluminum oxyhydroxides, nickel oxyhydroxides andlithium-cobalt oxyhydroxides.

For example, the oxide can be chosen from nickel-cobalt-manganeseoxides, nickel-cobalt-aluminum oxides, nickel oxide, lithiumnickel-cobalt-manganese oxides, lithium nickel-cobalt-aluminum oxides,lithium nickel oxide and lithium-cobalt oxides.

For example, the solid is a precipitate comprising the metal hydroxide,the precipitate being obtained at a pH of about 8 to about 14.

For example, the solid is a precipitate comprising the metal hydroxide,the precipitate being obtained at a pH of about 9 to about 13.

For example, the solid is a precipitate comprising the metal hydroxide,the precipitate being obtained at a pH of about 10 to about 12.

For example, the process further comprises washing the metal hydroxide.

For example, the process further comprises drying the metal hydroxide ata temperature of about 80° C. to about 130° C. or 90° C. to about 120°C.

For example, the metal sulfate is reacted with lithium hydroxide and achelating agent that is ammonia.

For example, the metal sulfate is reacted with lithium carbonate and achelating agent that is ammonia.

For example, the metal sulfate is reacted with lithium carbonate and achelating agent, that is ammonia hydrogen carbonate.

For example, the first metal can be chosen from nickel, cobalt,manganese, lithium and aluminum.

For example, the base can comprise at least one of LiOH. NaOH, KOH,RbOH, CsOH, Mg(OH)₂, Ca(H)₂, Sr(OH)₂ and Ba(OH)₂.

For example, the base can comprise at least one of be Li₂CO₃, Na₂CO₃,K₂CO₃, Rb₂CO₃, Cs₂CO₃, MgCO₃, CaCO₃, SrCO₃ and BaCO₃.

For example, the base can comprise at least one of LiHCO₃, NaHCO₃,KHCO₃, RbHCO₃, CsHCO₃, Mg(HCO₃)₂, Ca(HCO₃)₂, Sr(HCO₃)₂ and Ba(HCO₃)₂.

For example, the metal hydroxide can comprise at least one of LiOH,NaOH, KOH, RbOH, CsOH, Mg(OH)₂, Ca(CH)₂, Sr(OH)₂ and Ba(OH)₂.

For example, the second metal can be Li, Na, K, Rb, Cs, Mg, Ca, Sr, orBe.

For example, the third metal can be Li, Na, Ni, Co, Mn, Al, K, Rb, Cs,Mg, Ca, Sr, or Be.

For example, the third metal hydroxide can be LiOH.

For example, the another metal can be Li, Na, Ni, Co, Mn, Al, K, Rb, Cs,Mg, Ca, Sr, or Ba.

For example, the another metal hydroxide can be LiOH.

For example, the base can be purified before being reacted with themetal sulfate. For example, the base can be crystallized.

For example, the metal hydroxide produced by the electromembrane processcan be purified before being reacted with the metal sulfate. Forexample, the metla hydroxide can be crystallized.

For example, before submitting the liquid comprising sulfate to anelectromembrane in order to obtain an hydroxide, the sulfate can bepurified and/or concentrated.

For example, the chelating agent can be chosen from NH₃, NH₄OH,acetylacetone, 5-sulfosalicylic add, oxalic add.

For example, the chelating agent can be chosen from EDTA(ethylenediarninetetraacetic acid) NTA (nitniotriacetic acid), DGTA(trans-1,2-diaminocydohexanetetraacetic acid), DTPA (diethylene-triaminepentaacetic acid), and EGTA (ethylene glycol bis(2-aminoethylether)-N,N,N′,N′-tetraacetic acid)

For example, the chelating agent can be present.

For example, if the electromembrane process is a Na-based process, apurification step for the separation of lithium (in solution as lithiumsulfate) from the sodium sulfate solution can be carried out.

For example, sodium sulfate and lithium sulfate can be separated fromone another.

For example, sodium sulfate and lithium sulfate can be separated fromone another by means of a crystallization.

For example, the metal hydroxide can be NiCoAl(OH)₂ or NiMneo(OH)₂

For example, the metal hydroxide can be chosen fromNi_(0.8)Co_(0.15)Al_(0.05)(OH)₂, Ni_(0.8)Mn_(0.1)Co_(0.1)(OH)₂ andNi_(0.6)Mn_(0.2)Co_(0.2)(OH)₂.

For example, the metal oxide can be of formula LiMO₂, wherein M is atleast one metal chosen from nickel, cobalt, manganese, lithium andaluminum.

For example, the metal oxide can be of formula LiM₂O₄, wherein M is atleast one metal chosen from nickel, cobalt, manganese, lithium andaluminum.

For example the metal hydroxide or metal oxide can be of core-shelltype.

For example, the metal oxide can be chosen fromLiNi_(0.33)Mn_(0.33)Co_(0.33)O₂, LiNi_(0.5)Mn_(0.3)Co_(0.2)O₂,LiNi_(0.6)Mn_(0.2)Co_(0.2)O₂, LiNi_(0.8)Mn_(0.1)Co_(0.1)O₂ andLiNi_(0.8)Co_(0.15)Al_(0.05)O₂, or[LiNi_(x)M1_(y)M2_(z)O₂]_(core)/[LiNi_(a)M1_(b)M2_(c)O₂]_(shell), withM1=Mn, Co or Al and M2=Mn, Co or Al with x+y+z=1, a+b+c=1.

For example, the metal oxide can be, of formula LiMO2, orLi(1+x)M(1_(−x))O₂ for lithium-rich and Li_((1−z))M_((1+z)) forLi-deficient, wherein M can be at least one metal chosen from nickel,cobalt, manganese, lithium and aluminum.

For example, the lithium hydroxide obtained by the electromembraneprocess can be used as is in aqueous composition and reacted with theobtained metal hydroxide to obtain a mixture of metal hydroxides.

For example, the lithium hydroxide obtained by the electromembraneprocess can be crystallized before being reacted with the obtained metalhydroxide to obtain a mixture of metal hydroxides.

For example, the lithium hydroxide obtained by the electromembraneprocess can be crystallized and and then dissolved before being reactedwith the obtained metal hydroxide to obtain a mixture of metalhydroxides.

For example, the roasting of the mixture of metal hydroxides comprisesroasting at, a first temperature of at least 350° C. for a period oftime of at least about 4 hours.

For example, roasting the mixture of metal hydroxides comprises roastingat a first temperature of at least about 400° C. for a period of time ofat least about 6 hours.

For example, the process can further comprise roasting the mixture ofmetal hydroxides comprises roasting at a second temperature of at leastabout 600° C. for a period of time of at least about 6 hours.

For example, the process can further comprise roasting the mixture ofmetal hydroxides comprises roasting at a second temperature of at leastabout 700° C. for a period of time of at least about 8 hours.

For example, the process can further comprise roasting the mixture ofmetal hydroxides comprises roasting at a second temperature of at leastabout 500° C. for a period of time of at least about 8 hours.

For example, NH₃ can be, recovered in situ during mixture formation.

For example, the electromembrane process for converting Li₂SO₄ into LiOHcan be chosen from electromembrane processes as described in any one ofWO2013159194, WO2013177680, WO2014138933, WO 2015058287, WO2015058288,WO2015123762 and WO2017/031595. These documents are hereby incorporatedby reference in their entirety.

For example, carbonatation can be carried out as described inWO2013177680 or in WO2015058287, that are hereby incorporated byreference in their entirety.

The processes of the present disclosure can be operated, for example asa batch process. Alternatively, the processes of the present disclosurecan be operated as a semi-continuous process or a continuous process.

It will be appreciated by a person skilled in the art that one or moreparameters of the processes of the present disclosure such as but notlimited to pH, temperature, current density, voltage, current efficiencyand concentration can be monitored, for example by means known in theart. The selection of a suitable means for monitoring a particularparameter in a process of the present disclosure can be made by a personskilled in the art, Such parameters can also be maintained and/orchanged by a person skilled in the art, for example in light of theircommon general knowledge and with reference to the present disclosure.

The person skilled in the art would understand that various differentsources can bused for the metal sulfates. Metal sulfate(s) can bepurchased. Metal sulfates can also be obtained by leaching a metal or amixture of metals with H₂SO₄. Metal sulfate(s) can be obtained byleaching of spent lithium ion batteries. Metal sulfate(s) can beobtained by leaching a residue obtained after crushing spent lithium ionbatteries. Metal sulfate(s) can be obtained by leaching a residue aftertreatment of spent lithium ion batteries Metal sulfate(s) can forexample be derived from a mixture of transition metals that have beenleached. Metal sulfate(s) can be provided from a concentrate derivedfrom a mining company. Metal sulfate(s) can be obtained by leaching of anickel ore containing cobalt.

For example, during the electromembrane process consumption of thelithium sulfate to prepare lithium hydroxide can proceed to apre-determined extent.

For example, the composition comprising lithium sulfate can alsocomprise H₂SO₄.

For example, in the processes of the present disclosure, the aqueouscomposition comprising the lithium sulfate is submitted to anelectromembrane process under suitable conditions for conversion of thelithium sulfate to lithium hydroxide to proceed to a pre-determinedextent. The selection of a suitable pre-determined extent for aparticular process of the present disclosure can be made by a personskilled in the art. For example, the aqueous composition comprisinglithium sulfate is submitted to a electromembrane process under suitableconditions for consumption of the lithium sulfate to prepare lithiumhydroxide until one or more competing side reactions proceed to apre-determined extent, for example to an extent such that thepreparation of lithium hydroxide is no longer efficient.

For example, the electromembrane process is a two-compartment monopolaror bipolar membrane electrolysis process carried out in anelectrochemical cell comprising an anolyte compartment separated from acatholyte compartment by a cation exchange membrane, conversion of thelithium sulfate to lithium hydroxide can proceed until hydroxide currentefficiency is no longer efficient, for example hydroxide currentefficiency is no longer at least substantially maintained so that itdecreases. For example, the electromembrane process is a two-compartmentmonopolar or bipolar membrane electrolysis process carried out in aelectrochemical cell comprising an anolyte compartment separated from acatholyte compartment by a cation exchange membrane, conversion of thelithium sulfate to lithium hydroxide can proceed until pH in the anolytecompartment is a value of about 0.3 to about 1.4, about 0.4 to about1.2, about 0.4 to about 1.2, about 0.5 to about 0.8, about 0.5 to about0.7 or about 0.6.

For example, the electromembrane process is a two-compartment monopolaror bipolar membrane electrolysis process carried out in aelectrochemical cell comprising an anolyte compartment separated from acatholyte compartment by a cation, exchange membrane, conversion of thelithium sulfate to lithium hydroxide can proceed until consumption of, aparticular amount of the lithium sulfate comprised within the aqueouscomposition.

For example, the pre-determined extent can comprise consumption of about30 to about 60 weight % or of about 30 to about 50 weight % of thelithium sulfate comprised within the aqueous composition, based on thetotal amount of lithium sulfate contained in the aqueous composition.For example, the pre-determined extent can comprise consumption of about35 to about 45 weight % of the lithium sulfate comprised within theaqueous composition.

For example, the electromembrane process can comprise, consistessentially of or consist of a three-compartment membrane electrolysisprocess, for example a three-compartment monopolar or bipolar membraneelectrolysis process.

For example, the electromembrane process can comprise, consistessentially of or consist of a two-compartment membrane electrolysisprocess, for example a two-compartment monopolar or bipolar membraneelectrolysis process.

For example, the electromembrane process can comprise, consistessentially of or consist of a three-compartment membrane electrolysisprocess, for example a three-compartment bipolar membrane electrolysisprocess.

For example, the electromembrane process can comprise, consistessentially of or consist of a two-compartment membrane electrolysisprocess, for example a two-compartment bipolar membrane electrolysisprocess.

For example, the two-compartment membrane electrolysis process such asthe two-compartment monopolar or bipolar membrane electrolysis processcan be carried out in a electrochemical cell comprising an anolytecompartment separated from a catholyte compartment by a cation exchangemembrane.

For example, the cation exchange membrane can comprise, consistessentially of or consist of a perfluorosulfonic acid such as a Nafion™324 (or perfluorinate sulfonic acid), a cation exchange membrane orother membranes used for caustic concentration such as FuMA-Tech FKB orAstom CMB cation exchange membranes. The selection of a suitable cationexchange membrane for a particular process of the present disclosure canbe made by a person skilled in the art.

For example, during the two-compartment membrane electrolysis processsuch as the two-compartment monopolar or bipolar membrane electrolysisprocess, an aqueous stream comprising the lithium sulfate can beintroduced into the anolyte, compartment, the first lithium-reducedaqueous stream can be removed from the anolyte compartment and the firstlithium hydroxide-enriched aqueous stream can be removed from thecatholyte compartment.

For example, in the catholyte compartment of the two-compartmentmonopolar or bipolar membrane electrolysis process, lithium hydroxidecan be at least substantially maintained at a concentration of about 1 Mto about 4 M, about 2 M to about 4 M, about 2 M to about 3 M, about 2.5to about 3.5 M, about 2.8 to about 3.2 M or about 3 M.

For example, during the two-compartment monopolar or bipolar membraneelectrolysis process, the aqueous stream comprising the lithium sulfatecan be introduced into the anolyte compartment at a temperature of about10° C. to about 100° C., about 10° C. to about 100° C., about 10° C. toabout 90° C., about 20° C. to about 85° C., about 40° C. to about 80°C., about 40° C. to about 70° C., about 45° C. to about 60° C., about45° C. to about 55° C. or about 50° C.

For example, during the two-compartment monopolar or bipolar membraneelectrolysis process, the first lithium-reduced aqueous stream can beremoved from the anolyte compartment at a temperature of about 20° C. toabout 100° C., about 20° C. to about 85° C., about 50° C. to about 85°C. about 55° C. to about 65° C., about 45° C. to about 60° C. about 60°C. to about 85° C., about 70° C. to about 85° C. or about 80° C.

For example, during the two-compartment monopolar or bipolar membraneelectrolysis process, temperature in an electrochemical cell can be atleast substantially maintained at a value of about 60° C. to about 110°C., about 60° C. to about 100° C., about 60° C. to about 90° C., about60° C. to about 85° C., about 50° C. to about 85° C., about 50° C. toabout 70° C. about 55° C. to about 65° C., about 75° C. to about 85° C.or about 80° C.

For example, in the two-compartment monopolar or bipolar membraneelectrolysis process, current density can be at least substantiallymaintained at a value of from about 0.1 kA/m² to about 8000 kA/m², 0.5kA/m² to about 6 kA/m², about 1 kA/m² to about 6 kA/m², about 2 kA/m² toabout 6 kA/m² or about 3 kA/m² to about 5 kA/m², For example, currentdensity can be at least substantially maintained at a value chosen fromabout 3 kA/m², about 4 kA/m² and about 5 kA/m². For example, currentdensity can be at least substantially maintained at a value of about 4kA/m².

For example, in the two-compartment monopolar or bipolar membraneelectrolysis process, voltage can be at least substantially maintainedat a value of about 3 V to about 8 V, about 5 V to about 10 V, about 4 Vto about 6 V, about 4 to about 5 or about 4.5.

For example, the electrochemical cell can have a surface area of about0.2 m² to, about 4 m², about 0.5 m² to about 3.5 m², about 1 m² to about3 m² or about 1 m² to about 2 m².

For example, the electromembrane process can comprise, consistessentially of or consist of a two-compartment membrane electrolysisprocess, for example a two-compartment monopolar or bipolar membraneelectrolysis process.

For example, the electromembrane process can comprise, consistessentially of or consist of a three-compartment membrane electrolysisprocess, for example a three-compartment monopolar or bipolar membraneelectrolysis process.

For example, the three-compartment membrane electrolysis process such asthe three-compartment monopolar or bipolar membrane electrolysis processcan be carried out in a electrochemical cell comprising an anolytecompartment separated from a central compartment by an anion exchangemembrane and a catholyte compartment separated from the centralcompartment by a cation exchange membrane.

For example, the cation exchange membrane can comprise, consistessentially of or consist of a perfluorsulfonic acid such as a Nafion™324 cation exchange membrane or other membranes used for causticconcentration such as FuMA-Tech FKB or Astom CMB cation exchangemembranes. The selection of a suitable cation exchange membrane for aparticular process of the present disclosure can be made by a personskilled in the art.

For example, during the three-compartment membrane electrolysis processsuch as the three-compartment monopolar or bipolar membrane electrolysisprocess, the first lithium-reduced aqueous stream can be introduced intothe central compartment, the second lithium-reduced aqueous stream canbe removed from the central compartment and the second lithiumhydroxide-enriched aqueous stream can be removed from the catholytecompartment.

For example, the three-compartment membrane electrolysis process such asthe three-compartment monopolar or bipolar membrane electrolysis processcan further comprise producing an add such as sulfuric add in theanolyte compartment and removing an add-containing aqueous stream suchas a sulfuric add-containing aqueous stream from the anolytecompartment.

The selection of a suitable anion exchange membrane for a particularprocess of the present disclosure can be made by a person skilled in theart. For example, it will be appreciated by a person skilled in the artthat a proton-blocking membrane may, for example be useful in processescoproducing acids such as sulfuric add. For example, in thethree-compartment monopolar or bipolar membrane electrolysis process,the anion exchange membrane can be a proton-blocking membrane. Forexample, the proton-blocking membrane can such as a Fumatech FAB, AstomACM or Asahi AAV anion exchange membrane.

For example, in the anolyte compartment of the three-compartmentmonopolar or bipolar membrane electrolysis process, the add such assulfuric add can be at least substantially maintained at a concentrationof acid such as sulfuric add of about 0.1 M to about 2 M. For example,in the anolyte compartment of the three-compartment monopolar or bipolarmembrane electrolysis process, the sulfuric acid can be at leastsubstantially maintained at a concentration of sulfuric add can be about0.5 M to about 1.5 M, about 0.7 M to about 1.2 M, or about 0.8 M.

For example, in the catholyte compartment of the three-compartmentmembrane electrolysis process, the lithium hydroxide can be at leastsubstantially maintained at a concentration of about 1 M to about 5.0 M,about 1 M to about 4.0 M, about 1 M to about 3.0 M about 2 M to about3.0 M, about 1.5 M to about 2.5 M, about 1.8 M to about 2.2 M, or about2 M.

For example, during the three-compartment monopolar or bipolar membraneelectrolysis process, the first lithium-reduced aqueous stream can beintroduced into Hie central compartment at a temperature of about 20° C.to about 85° C., about 40° C. to about 85° C., about 40° C. to about 75°C., about 50° C. to about 70° C. about 50° C. to about 65° C. or about60° C.

For example, during the three-compartment monopolar or bipolar membraneelectrolysis process, the second lithium-reduced aqueous stream can beremoved from the anolyte compartment at a temperature of about 20° C. toabout 80° C. about 30° C. to about 70° C. about 40° C. to about 80° C.or about 60° C.

For example, during the three-compartment monopolar or bipolar membraneelectrolysis process, temperature in the second electrochemical cell canbe at least substantially maintained at a value of about 30° C. to about90° C., about 40° C. to about 85° C., about 50° C. to about 80° C.,about 50° C. to about 70° C. about 50° C. to about 65° C., about 50° C.to about 70° C. about 55° C. to about 65° C., or about 60° C.

For example, in the three-compartment monopolar or bipolar membraneelectrolysis process, current density can be at least substantiallymaintained at a value of about 0.5 kA/m² to about 5 kA/m² about 1 kA/m²to about 2 kA/m², about 3 kA/m² to about 5 kA/m², about 4 kA/m² or about1.5 kA/m².

For example, in the three-compartment monopolar or bipolar membraneelectrolysis process, voltage can be at least substantially maintainedat a value of about 5 V to about 9 V, about 6 V to about 8 V, about 6.5V to about 7.5 V or about 7 V.

For example, the electrochemical cell can have a cell area of about 0.2m² to about 4 m² about 0.5 m² to about 3.5 m², about 1 m² to about 3 m²or about 1 m² to about 2 m².

Alternatively, for example, in the processes of the present disclosure,the three compartment monopolar or bipolar membrane electrolysis processcan further comprise introducing ammonia into the anolyte compartmentproducing an ammonium compound such as ammonium sulfate in the anolytecompartment and removing an ammonium compound-containing aqueous streamsuch as an ammonium sulfate-containing aqueous stream from the anolytecompartment.

The selection of a suitable anion exchange membrane for a particularprocess of the present disclosure can be made by a person skilled in theart. For example, it win be appreciated by a person skilled in the artthat in processes that do not coproduce adds such as sulfuric add, ananion exchange membrane that is not a proton-blocking membrane may beuseful as it may, for example be able to withstand higher temperaturesand/or have lower resistance than a proton-blocking membrane. Forexample, in the three-compartment monopolar or bipolar membraneelectrolysis process, the anion exchange membrane may not be aproton-blocking membrane. For example, the anion exchange membrane canbe a such as an Astom AHA anion exchange membrane or FuMA-Tech FAP.

For example, in the analyte compartment of the three-compartmentmonopolar or bipolar membrane electrolysis process, the ammoniumcompound such as ammonium sulfate can be at least substantiallymaintained at a concentration of ammonium compound such as ammoniumsulfate of about 0.5 M to about 5 M, about 1 M to about 4 M or about 3M.

For example, in the catholyte compartment of the three-compartmentmonopolar or bipolar membrane electrolysis process, the lithiumhydroxide can be at least substantially maintained at a concentration ofabout 1 M to about 4.0 M, about 1.5 M to about 2.5 M or about 2 M.

For example, pH in the anolyte compartment of the two-compartmentmonopolar or bipolar membrane electrolysis process and/or the centralcompartment of the three-compartment monopoler or bipolar membraneelectrolysis process can be at least substantially maintained. Forexample, pH can be at least substantially maintained by adjusting atleast one of current density of the two-compartment monopolar or bipolarmembrane electrolysis process, current density of the three-compartmentmonopolar or bipolar membrane electrolysis process, flow rate of thefirst lithium-reduced aqueous stream and flow rate of the secondlithium-reduced aqueous stream.

For example, during the two-compartment monopolar or bipolar membraneelectrolysis process conversion of the lithium sulfate to lithiumhydroxide can proceed to a pre-determined extent.

For example, during the two-compartment monopolar or bipolar membraneelectrolysis process, en aqueous stream comprising the lithium sulfatecan be introduced into the anolyte compartment, the firstlithium-reduced aqueous stream can be removed from the anolytecompartment and the first lithium hydroxide-enriched aqueous stream canbe removed from the catholyte compartment; and during thethree-compartment monopolar or bipolar membrane electrolysis process,the first lithium-reduced aqueous stream can be introduced into thecentral compartment, the second lithium-reduced aqueous stream can beremoved from the central compartment and the second lithiumhydroxide-enriched aqueous stream can be removed from the catholytecompartment.

For example, the process n further comprise recycling at least a portionof the second lithium-reduced aqueous stream to the two-compartmentmonopolar or bipolar membrane electrolysis process.

It will be appreciated by a person skilled in the art that the processcan also be varied, as appropriate, using the examples discussed herein.

For example, at least a portion of the processes of the presentdisclosure can be operated as a batch process. Alternatively, forexample, the processes can be operated as a continuous processsemi-continuous process. For example, it would be appreciated by aperson skilled in the art that pH in the anolyte compartment of thetwo-compartment monopolar or bipolar membrane electrolysis processand/or the central compartment of the three-compartment monopolar orbipolar membrane electrolysis cell can be at least substantiallymaintained by adjusting the current density of the two-compartmentmonopolar or bipolar membrane electrolysis process and/or thethree-compartment monopolar or bipolar membrane electrolysis processand/or the flow rate of the streams flowing between the processes, forexample as described herein.

For example, pH in the anolyte compartment of the two-compartmentmonopolar or bipolar membrane electrolysis process and/or the centralcompartment of the three-compartment monopolar or bipolar membraneelectrolysis process can be at least substantially maintained.

For example pH can be at least substantially maintained by adjusting atleast one of current density of the two-compartment monopolar or bipolarmembrane electrolysis process, current density of the three-compartmentmonopolar or bipolar membrane electrolysis process, flow rate of thefirst lithium-reduced aqueous stream and flow rate of the secondlithium-reduced aqueous stream.

The selection of a suitable means for measuring and/or monitoring pH canbe made by a person skilled in the art. The selection of a suitablecurrent density and/or a suitable flow rate can be made by a personskilled in the art.

For example, the process can further comprise removing a firsthydrogen-containing stream from the catholyte compartment of theelectrochemical cell. For example, the process can further compriseremoving an oxygen-containing stream from the anolyte compartment of theelectrochemical cell.

For example, the electrochemical cell can further comprise means tomeasure pH in the anolyte compartment, and the system is configured toconvey the first lithium-reduced aqueous stream when pH in the anolytecompartment is below a pre-determined value.

For example, the electrochemical cell can further comprises means tomeasure pH in the central compartment, and the system is configured toconvey unconverted lithium sulfate from the central compartment of theelectrochemical cell when pH in the central compartment is above apre-determined value.

For example, the electrochemical cell can further comprises means tomeasure concentration of lithium hydroxide in the catholyte compartmentof the second electrochemical cell.

For example, lithium hydroxide can be crystallized as lithium hydroxidemonohydrate, optionally dried and reacted in solid state with theobtained metal hydroxide to obtain a mixture of metal hydroxides.

For example, the metal sulfates can be, obtained by leaching a battery.

For example, the battery can comprise LFP (LiFePO₄).

For example, lithium hydroxide can be concentrated before reacting itwith the metal hydroxide and to form the mixture of metal hydroxides.

For example, concentration can be carried out by using reverse osmosisor by heating.

For example, lithium hydroxide can be crystallized before reacting itwith the metal hydroxide and to form the mixture of metal hydroxides.

For example, the metal oxide can have the lamellar structure Li(M²⁺)O₂.

For example, the metal oxide can have the spinal structureLi(M^(x+))₂O₄, avec 3<X<4.

For example, the lithium hydroxide composition can be, concentratedbefore being reacted with the metal sulfate.

For example, concentration can be carded out by using reverse osmosis orby heating.

For example, the chelating agent can be NH₃.

For example, LiOH can be concentrated and then directly reacted with themetal hydroxide without crystallisation. For example, LiOH can beconcentrated, crystallized, optionally dried and then directly reactedwith the metal hydroxide.

For example, LiOH can be treated with a flash dryer.

For example LiOH and the metal hydroxide can be reacted together toobtain a mixture and then heated together.

For example LiOH and the metal hydroxide can be reacted together toobtain a mixture and then heated together in a spray dryer.

For example, crystals of lithium sulfate monohydrate can be insertedinto the cell so as to increase concentration Li₂SO₄.

For example, the sulfate or hydroxide can be purified by a solventextraction method. For example, the solvents used for solvent extractioncan be, based on phosphorous acid e.g. Cyanex 272, Cyanex 301, Cyanex302, Di-(2-ethylhexyl)phosphoric acid (D2EHPA), DEHTPA, Saysolvex DEDP,lonquest 801, Hoe F 3787, MEHPA, P204, PC88A, P507, or hydroxy-oximeextractants (e.g. Acorga P50, Awrga K2000, LIX 84-I, SME 529, LAX 65N,LAX 64, LAX 70, LIX 860, UX 622), or β-diketone metal cation extractants(e.g. LIX, 54, XI-N54, XI-55, XI-57) [Source: Solvent extraction: thecoordination chemistry behind extractive metallurgy. Chem, Soc. Rev.,2014, 43, 123].

For example, the filtered sulfate solution after the co-precipitation ofthe hydroxide could optionally be purified and/or concentrated beforeentering the membrane electrolysis.

For example, the leached solution can be purified before the coprecipitation of the hydroxide. Examples of purification can be relatedto metals selective separation, e.g., precipitation of hydroxides,precipitation of insoluble salts, oxidative precipitation, ion exchange,solvent extraction, electrochemical plating, crystallization.

For example, selective precipitation can be performed by addition ofe.g. O₂, SO₂ or H₂SO₅, persulfates ((NH₄)₂S₂O₈), ammonium oxalate(NH₄)₂C₂O₄, chlorine, chlorine compounds (HCl, ClO₂, HClO₃), O₃, NaOCl,CoS, Na₂S, NaHS. CaCO₃, Na₃PO₄.

For example, precipitation of hydroxides can be obtained by addition ofe.g. LiOH, NaOH, NH₄OH.

For example, precipitation of insoluble salts can be obtained byaddition of dimethylglyoxime.

For example, the LiPF₆ electrolyte can be recovered.

For example, the solid/liquid (gram of material/volume of liquid) ratioin g/L for the leaching step can be comprise between 1/5 to 1:100.

For example, the leaching solution can be a mixture of at least one ofH₂SO₄, H₂O₂, HNO₃, HCl, nitric add, citric acid, oxalic acid, asparticacid, ascorbic acid, glucose.

For example, the sulfate metals M(SO₄) (with M=Ni, Co, Mn) and/orAl₂(SO₄)₃ can be optionally crystallized before being used as precursorin the synthesis of the hydroxide.

For example, even though the final material was obtained here usingco-precipitation method, any other kind of synthesis method leading tothe synthesis of a layered oxide material with recycling oflithium-containing sulfate solution is encompassed within the scope ofthe present disclosure

According to one example, a process according to the present disclosureis presented in FIG. 1. As it can be seen from FIG. 1, nickel sulfate,cobalt sulfate and manganese sulfate can be mixed together to obtain acomposition comprising various metal sulfates. Such a composition can bean aqueous composition, for example, an acidic aqueous composition. Forexample, a material comprising at least one metal can be leached withH₂SO₄, thereby obtaining the desired metal sulfates composition.Alternatively, various metal sulfates can be reacted with an aqueousacidic composition to obtain the desired metal sulfates composition,LiOH and a chelating agent (for example NH₃) are then added to thismixture to get the mixture formation and eventually to precipitate thedesired metal hydroxide. LiOH is a pH enhancer as the sulfate metalreaction starts at high pH, and NH₃ can act as a chelating agent. Oncethe reaction starts, a solid phase will precipitate (i.e. being thehydroxide compound) and can be separated from the liquid phase at highpH, e.g. 10≤pH≤13. This solid phase precipitate will be further washedwith water and dried out at 120° C. for 8 h under air. Then, thehydroxide phase NMC(OH)₂ is obtained. The liquid phase gathered earliercontains dissolved Li₂SO₄, which can be collected after liquid phasefiltration. This Li₂SO₄ lithium sulfate can be electrolyzed in amembrane electrolyser into lithium hydroxide LiOH, that could be used aspH enhancer for another mixture formation.

The person skilled in the art would understand that the electromembraneprocess can be carried in many different manners and in accordance tovarious different parameters. For example, such an electromembraneprocess can be carried as defined in any one of the following referencesWO2013159194, WO2013177680, WO2014138933, WO 2015/058287, WO2015/058287, WO 2015/123762, WO2017031595 and WO2018035618. Thesedocuments are hereby incorporated by reference in their entirety.

The hydroxide phase NMC(OH)₂ can be further used to be mixed with LiOHobtained from electrolysis of the Li₂SO₄ to obtain a mixture of metalhydroxides. For example, this mixture of metal hydroxides can be roastedat different temperatures. For example, it can be roasted, at a firsttemperature of 450° C. for about 8 h under air, then it can be roastedat 800° C. for 12 h under air. Then, it is crushed and sieved, washedwith water, and finally dried at 600° C. for about 8 h under air. Thenickel-manganese-cobalt lithium oxide Li—(Ni_(x)Mn_(y)Co_(z))O₂ is thenobtained, wherein 0<x, y, z<1 and x+y+z=1. Core-shell materials can alsobe obtained, with a gradient concentration from the core to the surfacefor the different metals,[LiNi_(x)M1_(y)M2_(z)O₂]_(core)/[LiNi_(a)M1_(b)M2_(c)O₂]_(shell), withx+y+z=1, a+b+c=1, M1=Mn, Co or Al and M2=Mn, Co or Al, and e.g. a≠x forNi being different, leading to the concentration gradient in the finalmaterial.

For example, the metal source can be an at least substantially puremetal leached by the electrochemically generated sulfuric acid.

For example, the metal source can be a nickel concentrate (containingalso cobalt and possibly other elements) leached by theelectrochemically generated sulfuric acid.

For example, the metal source can be a nickel cobalt containing material(e.g. nickel oxide ore, nickel matte, nickel sulfide, mixed sulfide ofnickel and cobalt, crude nickel sulfate produced from a copper smeltingprocess, and nickel oxide) leached by the electrochemically generatedsulfuric acid.

For example, the metal source can be an aqueous nickel-cobalt solutionsuch as the solutions referred as C or D in FIG. 31, FIG. 32 and FIG.33, leached by the electrochemically generated sulfuric acid.

For example, the metal source can be an organic solution containingnickel (and cobalt and possibly other elements) that can be stripped bythe electrochemically generated sulfuric acid.

For example, the metal source can be a spent battery leached orconstituent thereof (e.g. cathode, anode, black mass, slag, or mixturesthereof) (e.g. the cathode only, or both the anode and the cathode or ablack mass, etc) leached by the electrochemically generated sulfuricacid.

The person skilled in the art would understand that the process shown inFIG. 1 can vary in accordance with the nature of the at least one metalsulfate used as starting material. Various metals can thus be used andvarious mixtures thereof as starting material.

EXAMPLES

Synthesis of Oxides at High Potential for Cathode Material of LithiumIon Batteries

A cathode material was synthetized to produce a lithium transition metaloxide with specific formula. Li_(p)Ni_(x)Mn_(y)Co_(z)Al_(q)O₂. Theformula has specific percentage to reach certain kind of materials inthe industries. The obtained cathodes materials are LiCoO₂,LiNi_(0.8)Co_(0.15)Al_(0.05)O₂; LiNi_(0.8)Mn_(0.1)Co_(0.1)O₂ andLiNi_(0.6)Mn_(0.2)Co_(0.2)O₂.

Example 1 Synthesis of Co(OH)₂

28.11 g of CoSO₄.7H₂O (Strem Chemicals, inc) was dissolved in 100 mL ofdistilled water to produce a solution of 1M (pH around 4-5). 10.49 g ofLiOH.H₂O (Sigma-Aldrich) was dissolved in 250 mL of distilled water toobtain a solution of 1M (pH over 12). 5.841 mL was taken of a solutionof 28-30% vol of ammonia (Sigma-Aldrich) to have a solution of 2M(pH>12).

The montage was built with a flask round bottom 4-neck (Dima glass inc).One of the neck was used for a nitrogen flow to have an inert atmospherein the flask. Two other opening were used to pour LiOH and NH₃ and thefourth one was dedicated to the recovery of NH₃ through a condenser.

The montage was set with the solution of CoSO₄ at the bottom of theflask, 10 mL of the solution of CoSO₄ 1M was first of all deaerated by aflow of nitrogen and the system was maintained under a nitrogen flow for15 minutes. The temperature was regulated at 60° C. 20 mL of NH₃ and 25mL of LICH were introduced drop by drop and the solution was maintainedin the flask with a constant stirring. The reaction began when the pH ofthe solution reached 10. Once the products reacted (i.e. after 10minutes), the solution was stirred for another 20 minutes. The substratewas filtered and washed three times with distilled water.

After filtration, the sample was heated at 120° C. for 8 hours. Then, 1g of the Co(OH)₂ was collected (pink color). The overall reaction isgiven Equation 1.

CoSO₄+2LiOH+NH₃→Co(OH)₂+Li₂SO₄+NH₃   Equation 1

In this equation, all the reagents are in aqueous solution. The cobalthydroxide, product of the reaction in Equation 1, will be used asprecursor for the synthesis of the cobalt oxide (cf. example 2). In themother liquor, an aqueous solution of Li₂SO₄ was mixed with a leftoverof LiOH, excess during the reaction, To convert all the LION intolithium sulfate, the solution was neutralized using 1-12504 as showed inEquation 2.

2LiOH+H₂SO₄→Li₂SO₄.H₂O+H₂O   Equation 2

The filtrated Li₂SO₄ can be electrolysed and converted into. LiOH.H₂O.X-ray diffraction was performed on the compound to highlight its highpurity.

FIG. 2 represents the X-Ray diffraction pattern of the Co(OH)₂. It maybe indexed with the theoretical diffraction peaks of the cobalthydroxide. Besides, an impurity can be notice, as a small intensity peakis observed at 20°. In the synthesis of the hydroxide, LiOH is used as asource of pH enhancer, as the formation reaction of the hydroxide startsat high pH. For example, LiOH can be replaced by NaOH and X-raydiffraction was performed on the compound to highlight its high purity.In such a case, the electromembrane process can be used for convertingNa₂SO₄ into NaOH.

FIG. 3 represents the X-Ray diffraction pattern of the Co(OH)₂ synthesiswith NaOH as pH enhancer source. The X-Ray diffraction pattern of thecompound may be indexed with the theoretical diffraction peaks of thecobalt hydroxide. Besides, an impurity can be notice, as a smallintensity peak is observed at 20° as was observed for the LiOHdiffractogram.

This Co(OH)₂ material based on NaOH or LiOH as pH enhancer source wasthe precursor of various potential products (see below).

Example 2 Synthesis of LiCoO₂

The cobalt hydroxide previously obtained was used as, precursors for thesynthesis of the lithium cobalt oxide, LiCoO₂. Here, the first step wasto mix the LiOH.H₂O with the Co(OH)₂. This was a stoichiometric reactionas show in Equation 3

Co(OH)₂+LiOH.H₂O+0.250₂→LiCoO₂+2.5H₂O   Equation 3

The precursors were mixed, crushed, and pellets were done before thermaltreatment. These pellets were put in the furnace for 8 hours at 450° C.under air. After this step, the pellets were crushed and redone inpellets. The furnace was now set at 800° C. for 12 hours under air. Thepellets were crushed again and then washed with water. The suspensionwas filtered, the powder collected and pressed in pellets again. Thefinal step consisted in another thermal treatment for 8 hours at 600° C.under air.

The X-ray diffraction pattern in confirmed the high purity of thelithium cobalt oxide.

FIG. 4 presents the X-Ray diffraction pattern of the lithium cobaltoxide. One can see an impurity at 20°, that may be a residue of cobalthydroxide (the same impurity was observed). This impurity has alreadybeen reported several times in the literature.

The lithitated cobalt oxide can also be produced from the cobalthydroxide obtained with NaOH. The X-Ray diffraction of such compound canbe found in FIG. 5 and pointed out that no difference is observeddepending on the nature of the base source during the hydroxidesynthesis.

The next step was to characterize the LiCoO₂ with the electrochemistry.The cathode electrode was prepared by mixing 83 wt. % of LiCoO₂, 9 wt. %of carbon black Timcal C65, and wt. % of polyvinylidene difluoride(PVDF) in n-methyl pyrrolidone (NMP) solvent to form a slurry. Theslurry was mixed for few hours to homogeneity and spread on acarbon-coated aluminum foil using the doctor blade method. After dryingat 70° C. in a vacuum oven overnight, electrode disks of 0.5±0.1 mg/cm2of active material loading were cut and calendered. Standard coin-cells(2032) were assembled in an Ar-filled glove box. Once the electrode wasprepared, a lithium foil was used as the anode. 1 M LiPF6 dissolve inethylene carbonate and diethyl carbonate (1:2 volume ratio) solvents wasused as liquid electrolyte. Polypropylene membranes (Celgard inc.) wereused as separators. The electrochemical tests were performed on thecells at 30° C. on a VMP electrochemical station (Bio-Logic, France)with cut-off voltages of 3 and 4.3 V vs Li/Li+ at 0.1 C rate forgalvanostatic cycling. Three coin cells were prepared per sample toensure reproducibility of the results. The standard deviation wasdetermined to be ±1 mAh/g.

FIG. 6 showed the five first charges and discharges of the LiCoO₂. Thecapacity reached 175 mAhg⁻¹ but decrease with the cycling. The capacityof the LiCoO₂ change Depending of the potential range but at higherpotential, irreversible reaction could happen. However, at 4.3 V, thecompound should be stable. Some optimization should be done to optimizethe capacity and the stability of the LiCoO₂.

Example 3 Synthesis of Ni_(0.8)Co_(0.15)Al_(0.05)(OH)₂

2.3121 g of NiSO₄.6H₂O (Strem Chemicals, inc), 0.4628 g of CoSO₄.6H₂O(Strem Chemicals, inc) and 0.0944 g of Al₂(SO₄)₃.H₂O (Sigma-Aldrich)were dissolved in 10 mL of water.

The montage and the reaction condition were as described in Example 1.The final product gave Ni_(0.8)Co_(0.15)Al_(0.05)(OH)₂ with a greencoloration. X-ray diffraction pattern confirmed the formation of thehydroxide, as the diffraction pattern presented in FIG. 7 may fit withthe theoretical diffraction pattern of Ni_(0.8)Co_(0.15)Al_(0.05)(OH)₂(vertical bars).

Example 4 Synthesis of LiNi_(0.8)Co_(0.15)Al_(0.05)O₂

The next experimental was the formation of theLiNi_(0.8)Co_(0.15)Al_(0.05)O₂. The experimental procedure was the sameas in example 1. X-ray diffraction was used to characterize theformation of the oxide.

FIG. 8 highlights that the diffraction pattern of the compound may fitwith the theoretical diffraction peaks ofLiNi_(0.8)Co_(0.15)Al_(0.05)O₂. The last characterization was theelectrochemistry of the compound.

FIG. 9 showed the charge and discharge of theLiNi_(0.8)Co_(0.15)Al_(0.05)O₂ at 0.1C rate. The electrochemistryprocedure was detailed in example 2. The theoretical capacity of thiscompound is 279 mAh/g and the specific capacity obtained experimentallywas 180 mAh/g. On FIG. 9, one can see two slopes in the discharge curve.This behaviour can be explained by the size particles of the activematerial, being wide and not optimized for electrochemistry purpose.

Example 5 Synthesis of Ni_(0.8)Mn_(0.1)Co_(0.1)(OH)₂

2.3131 g of NiSO₄.6H₂O (Strem Chemicals, inc), 0.3092 g of CoSO₄.6H₂O(Strem Chemicals, Inc) and 0.18598 of MnSO₄.H₂O (Sigma-Aldrich) weredissolved in 10 mL of water.

The montage and the reaction condition were as described in example 1.

FIG. 10 highlights that the diffraction pattern of the compound may fitwith the theoretical diffraction peaks of Ni_(0.8)Mn_(0.1)Co_(0.1)(OH)₂.

Example 6 Synthesis of LiNi_(0.8)Mn_(0.1)Co_(0.1)O₂

The next step was the formation of the oxide,LiNi_(0.8)Mn_(0.1)Co_(0.1)O₂. The experimental set-up was the same as inexample 2. X-ray diffraction was used to characterize the formation ofthe oxide.

FIG. 11 highlights that the diffraction pattern of the compound may fitwith the theoretical diffraction peaks of LiNi_(0.8)Mn_(0.1)Co_(0.1)O₂.

The capacity reached 175 mAhg⁻¹ but decrease with the cycling. Thecapacity of the LiCoO₂ change depending of the potential range but athigher potential, irreversible reaction could happen.

Example 7 Synthesis of Ni_(0.6)Mn_(0.2)Co_(0.2)(OH)₂

1.7348 g of NiSO₄.6H₂O (Strem Chemicals, inc), 0.6184 g of CoSO₄.6H₂O(Strem Chemicals, inc) and 0.3674 g of MnSO₄.H₂O (Sigma-Aldrich) wasdissolved in 10 of water.

The montage and the reaction condition were as described in example 1.

FIG. 12 shows highlights that the diffraction pattern of the compoundmay fit with the theoretical diffraction peaks ofNi_(0.6)Mn_(0.2)Co_(0.2)(OH)₂.

Example 8 Synthesis of LiNi_(0.6)Mn_(0.2)Co_(0.2)O₂

The next step was the formation of the oxide,LiNi_(0.6)Mn_(0.2)Co_(0.2)O₂. The experimental step was the same as theexample 2. X-ray diffraction was used to characterize the formation ofthe oxide.

FIG. 13 highlights that the diffraction pattern of the compound may fitwith the theoretical diffraction peaks of LiNi_(0.6)Mn_(0.2)Co_(0.2)O₂.

FIG. 14 represents the charge/discharge curves ofLiNi_(0.6)Mn_(0.2)Co_(0.2)O2 at 0.1C rate. The electrochemistryinstrument and method were as described in example 2. The theoreticalcapacity of this compound is 275 mAh/g and the specific capacityobtained experimentally was 170 mAh/g. On FIG. 14, one can see twoslopes in the discharge curve. This behaviour can be explained by thesize particles of the active material, being wide and not optimized forelectrochemistry purpose.

Example 9 Electrolysis of Lithium Sulfate and Conversion into LithiumHydroxide

Electrolysis of lithium sulfate was carried out in a two-compartmentcell ICI FM-21 (similar to the cell of FIG. 2 of WO2015058287) byfollowing the general procedure described in Example 1 of WO2015058287.The experimental conditions were as follows

-   -   Cell: FM-21 2400 cm²    -   Current density: 4.0 kA/m²    -   Temperature: 60° C.    -   Li₂SO₄:300 g/L (batch)    -   LiOH.H₂O:2 M

The results obtained were as follows:

-   -   Conversion rate 40%    -   H₂SO₄:10.2%    -   Current, efficiency: 76.9%    -   Flow rate LiOH: 14.4 L/h    -   Productivity 4.75 kg of LiOH.H₂O/h/m²    -   Voltage (at the cell): 4.39 V    -   Energy: 3678 kWh/TM LiOH.H₂O

FIGS. 1 to 22 show the results obtained during electrolysis of Li₂SO₄.

FIG. 15 is a plot showing sulphuric acid concentration in e anolytestream as a function of batch time; FIG. 16 is a plot showing anolyteand catholyte conductivities as a function of batch time; FIG. 17 is aplot showing anolyte and catholyte temperature as a function of batchtime; FIG. 18 is a plot showing voltage at cell and at current generatoras a function of batch time; FIG. 19 is a plot showing productivity inmilliliters of lithium hydroxide monohydrate equivalent per minute as afunction of sulfuric acid concentration in the anolyte; FIG. 20 is aplot showing productivity in liters of lithium hydroxide monohydrateequivalent per hour as a function of sulfuric acid concentration in theanolyte; FIG. 21 is a plot showing current efficiency as a function ofsulfuric acid concentration in the anolyte; FIG. 22 is a plot showingproductivity in kilograms of lithium hydroxide monohydrate equivalentper hour per meter square of electroactive area as a function ofsulfuric acid concentration in the anolyte; FIG. 23 is a plot showingelectric energy consumption related to the electrochemical conversion inkilowatt-hour per, metric ton of lithium hydroxide monohydrateequivalent as a function of sulfuric acid concentration in the anolyte.

As shown in FIG. 24 LiOH can be added as a source of pH enhancer to amixture of metal sulfate(s) for the precipitation of the metalhydroxide(s) After precipitation of the metal hydroxide(s). Li₂SO₄ canbe recovered as a dissolved species in aqueous solution to be insertedin the membrane electrolyser, and can be converted into LiOH andoptionally going through evaporation, crystallization and drying beforereacting with a metal hydroxide(s) to form a metal oxide(s). Sulfuricacid is used for the leaching of the transition metal source, generatingmetals as dissolved species in sulfate forms.

As shown in FIG. 25 NaOH can be added as a source of pH enhancer to amixture of metal sulfate(S) for the precipitation of the metalhydroxide(s). After precipitation of the metal hydroxide(s), Na₂SO₄ canbe recovered as a dissolved species in aqueous solution to be insertedin the membrane electrolyser. LiOH can be reacted with a metalhydroxide(s) to form a metal oxide(s). If Lithium is present in theTransition Metal Source, it will be carried out in the metal sulfatesolution, the obtained Li2SO4 can be separated from Na2SO4 to purify theNa2SO4 solution before being inserted in the membrane electrolyser. TheLiOH used to react with the Lithiated Metal oxide can come from anotherelectromembrane process, or be a commercial LiOH.

As shown in FIG. 26, a mixture of NaOH and LiOH is used as a source ofpH enhancer to a mixture of metal sulfate(s) for the precipitation ofthe metal hydroxide(s) After precipitation of the metal hydroxide(s), amixture of Li₂SO₄ and Na₂SO₄ can be recovered as dissolved species inaqueous solution to be inserted in the membrane electrolyser, and Li₂SO₄can be converted into LiOH to react with a metal hydroxide(s) to form ametal oxide(s), LiOH can be separated from NaOH. For example, LiOH canbe substantially selectively precipitated (for example via evaporation,crystallization and drying step) over NaOH and thus separated therefrom.Also, Li2SO4 can be optionally separated from Na2SO4 before reacting inthe electromembrane process. The obtained LiOH can be reacted with so asto eventually be used to generate metal oxide(s) by reacting with themetal hydroxide(s) to form a metal oxide(s).

As shown in FIG. 27 NaOH can be added as a source of pH enhancer to amixture of metal sulfate(s) for the precipitation of the metalhydroxide(s). For example, NaOH can be used instead of LiOH as a pHenhancer because of economical reasons. After precipitation of the metalhydroxide(s), a mixture of Li₂SO₄ and Na₂SO₄ can be recovered as adissolved species in aqueous solution to be inserted in the membraneelectrolyser, and Li₂SO₄ can be converted into LiOH to react with ametal hydroxide(s) to form a metal oxide(s), LiOH can be substantiallyselectively precipitated (for example via evaporation, crystallizationand drying, step) over NaOH. The obtained LiOH can be reacted with so asto eventually be used to generate metal oxide(s) by reacting with themetal hydroxide(s) to form a metal oxide(s). The person skilled in theart would understand that if for example the transition metal source isa spent battery, it can be possible that 100% of the lithium containedtherein will not necessarily be electrolyzed and thus, an externalsource of Li₂SO₄ can be provided to the electromembrane process to beconverted into LiOH.

As shown in FIG. 28, the LiOH used for the precipitation of thehydroxide can be optionally crystallized. Moreover, the lithium sulfatesolution can be purified and concentrated before being inserted inelectromembrane process. For example, an external source of Li₂SO₄ canbe provided in the present case. In fact, since LiOH generated is usedfor (i) reacting with the metal sulfate and (ii) to be mixed with theobtained metal hydroxide(S) an external source of Li₂SO₄ cal beprovided.

As shown in FIG. 29, the electrochemically generated sulfuric addsolution, called the anolyte solution, can be concentrated to leach thetransition metal source, e.g. a battery active material.

The anolyte concentration process described in FIG. 29 can be Gamed outby a method or process as described in any, one of WO2015123762,WO2017031595 and WO2018035618. These documents are hereby incorporatedby reference in their entirety. The person skilled of the art can willunderstand that the anolyte concentration from FIG. 29 can therefore beapplied in any of FIG. 24 to FIG. 28. The Anolyte solution afterconcentration will be lithium-depleted, and the Li2SO4 rich solutionwill be inserted back in the electromembrane system to be processed. Thelithium sulfate solution obtained after anolyte concentration can bemixed with the Li₂SO₄ solution recovered after hydroxide precipitationas described in FIG. 29. Such Mixture of Li₂SO₄ solutions can bereturned to the electromembrane process.

FIG. 30 describes the synthesis of a core-shell design material. Themetal hydroxide with a core-shell design can be precipitated asdescribed from FIG. 24 to FIG. 29 and the lithiated material core-shelloxide can be obtained after addition of LiOH.

From FIG. 28 to FIG. 29, the person skilled of the art cart understandthat LiOH optionally crystallized can be replaced by NaOH or a mixtureof both to enhance the pH. Same apply for Li₂SO₄ that could be replacedby Na₂SO₄ or a mixture of both. The person skilled of the art can alsounderstand that the concentration and purification of the sulfatesolution as describe in FIG. 29 can be applied for any processes fromFIG. 24 to FIG. 30.

FIG. 31 describes the precipitation of metal carbonates instead of metalhydroxides. To do so, the LiOH as generated from the membraneelectrolysis can be carbonated to form Li₂CO₃. For example,carbonatation can be carried out as described in WO2013177680,WO2008104367, WO2018134536 or in WO2015058287, that are herebyincorporated by reference in their entirety. This lithium carbonate canreact with the metal sulfate to form the metal carbonate. A lithiumsulfate solution will be recovered as described in FIGS. 24 to 30.

The person skilled of the art will understand that all the possibleembodiment described from FIG. 24 to FIG. 31 can also be applied in FIG.32 replacing sulfate by nitrate (e.g. concentration of Li₂SO₄ solutionand/or Li₂SO⁴ and mixture with Na₂SO₄).

Besides, the person skilled of the art can understand that LiOH cart bereplaced by NaOH or a mixture of both in any of FIG. 24 to FIG. to FIG.31. Same apply for Li2SO4 that could be replaced by Na2SO4 or a mixtureof both.

From FIG. 24 to FIG. 31, various sources of add solution can be used forthe reaction with the Transition Metal source, for example it can besulfuric acid solution (FIG. 24), lithium sulfate solution (FIG. 29),and anolyte solution. For example, these various sources of acidsolution for the leaching solution can be: (A) Electrochemicallygenerated sulfuric add solution, called anolyte solution: (B) Partiallyconcentrated sulfuric acid solution generated by membrane electrolysis,called (diluted) Lithium Sulfate solution or (C) Sulfuric acid. The (a)anolyte solution relates to an electrochemically generated sulfuric acidsolution from a membrane electrolysis, having the chemical compositionas presented in Table 1. The concentration of this solution was ≈1.5 MH₂SO₄.

TABLE 1 Composition of the electrochemically generated sulfuric acidsolution as it exists in the membrane electrolysis. Percentages (wt %)Li₂SO₄ 10-20 H₂SO₄ 10-15 H₂O 65-75

The (b) partially concentrated sulfuric acid solution generated bymembrane electrolysis, called (diluted) Lithium Sulfate solution,consists of the previous anolyte solution depleted in lithium,concentrated and then diluted in water to reach a concentration of ≈1 MH₂SO₄.

From FIG. 32, nitric acid can be generated from the salt splitting ofLiNO3 used instead of Li2SO4, The leaching of the transition metalsource with nitric acid will lead to the production of metal nitratesdissolved in solutions. Then, LiOH is added for the precipitation of thehydroxide, and a nitric lithiated solution can be filtrate. This LiNO3solution can enter the electromembrane process to be converted into LiOHand HNO3. All the embodiments of FIG. 24 to FIG. 31 apply here whenreplacing sulfate by FIG. 32.

The overall protocol starting from the Ni and Co concentrate isillustrated in FIG. 33, FIG. 34, FIG. 35, and can lead to the productionof high purity Co and Ni aqueous phases (called solution A and B in FIG.33, FIG. 34, FIG. 35), to the production of high purity Co or Ni aqueoussolutions (called C and D), or to the cobalt sulfate or nickel sulfatecrystallized salts (called E and F). For example, the pH is increasedfrom solution A to B to ensure a maximum recovery of the cobalt in theorganic phase. For example, Lithium Sulfate solution can be provided bythe anolyte solution as generated by the electromembrane process, andconcentrated as described in FIG. 29

From FIG. 33 to FIG. 35, various sources of acid solution can be usedfor the leaching of the Li—Co concentrate, for example it can besulfuric acid solution (FIG. 33), lithium sulfate solution (FIG. 34),and anolyte solution (FIG. 35).

The person skilled in the art would understand that for example theembodiments provided in FIG. 33 to FIG. 35 can be applicable in theprocesses shown FIG. 24 to FIG. 31, and meta sulfates obtained in FIG.33 to FIG. 35 can be the source of the Transition Metal box from FIG. 24to FIG. 31. Besides, the sulfate acid source used for the leaching inFIG. 33 to FIG. 35 could be replaced by nitric to obtain a transitionmetal source in form of a nitrate as described in FIG. 32.

The person skilled of the art would understand that LiOH used in FIG. 24to FIG. 30 and in FIG. 34 to react with the metal hydroxide/carbonate tofrom the lithiated metal oxide(s) can be carbonated, generating Li₂CO₃reacting with the metal hydroxide/carbonate to form the lithiated metaloxide(s). Other carbonates as described in the present disclosure canalso be used such as Na₂CO₃, K₂CO₃, Rb₂CO₃, Cs₂CO₃, MgCO₃, CaCO₃, SrCO₃or BaCO₃

The person skilled of the art would understand that nitrates used inFIG. 35 can be an alternative to sulfates as presented in FIG. 24 toFIG. 34, and all the processes presented in FIG. 24 to FIG. 34 can beused replacing sulfates by nitrates.

For example, conversion from metal carbonates to lithium oxide isdescribed in WO2006104367, that is hereby incorporated by reference inits entirety.

For example, the electrochemically generated sulfuric acid (H₂SO₄solution) generated in FIGS. 24 to 28 can contain lithium sulfate,sodium sulfate and/or potassium sulfate. H₂SO₄ can be separated fromlithium sulfate, sodium sulfate and/or potassium sulfate as shown inFIG. 29 through anolyte concentration. For example, such a separationcan be achieved by a elective crystallization of a sulfate monohydrate.For example, anolyte concentration can be carried out by selectivesulfate precipitation as defined in any one of WO2015123762,WO2017031595 and WO2018035618. These documents are hereby incorporatedby reference in their entirety.

Besides, the person skilled of the art can understand that the acidsolution generated by electromembrane process in FIG. 24 to FIG. 35 canbe replaced by the anolyte solution and a concentration step aspresented in FIG. 29.

The person skilled of the art will understand that all the possibleembodiment described from FIG. 24 to FIG. 34 can also be applied in FIG.35 (e.g. concentration of Li₂SO₄ solution and/or Li₂SO₄ and mixture withNa₂SO₄).

Example 10—Core-shell Synthesis

For the synthesis of a gradient concentration material with acomposition Li[Ni_(d)M1_(e)M2_(r)]O₂ with d+e+f=1 being made of a[LiNi_(x)M1_(y)M2_(z)O₂] with x+y+z=1 and a shell[LiNi_(a)M1_(b)M2_(c)O₂] with a+b+c=1, with M1=Mn, Co or Al and M2=Mn,Co or Ai and with x<d<a, y<e<b, z<f<c. In order to prepare such aspherical Core-Shell material, the hydroxide precursor has to beobtained first, and can be synthetized via co-precipitation. In such asynthesis method, a certain amount of NiSO₄.6H2O (and optionally M1 at agiven concentration and M2 at a different concentration) aqueoussolution was used as starting material for the core composition ofNi_(x)M1_(y)M2_(z)(OH)₂. The metal aqueous solution, were continuouslyfed into a batch reactor already filled with certain amounts ofdeionized water, NaOH_((ag.)) as pH enhancer and NH₄OH_((aq.)) aschelating agent, under a nitrogen atmosphere. Simultaneously, NaOH at agiven concentration and adequate amount of NH4OH_((aq.)) were pumpedinto the reactor. Once the precursor Ni_(x)M1_(y)M2_(z)(OH)₂ is formedin solution, the second solution, an aqueous solution of the desiredmetals Ni_(a)M1_(b)M2_(c)(OH)₂ (e.g. M1 and M2=Ni, Mn, Co, Al) wasintroduced into the reactor. The obtained Ni_(d)M1_(e)M2_(f)(OH)₂ (withx<d<a, y<e<b, z<f<c) powders were filtered, washed, and dried undervacuum at 110° C. for 12 h. To prepare Li[Ni_(d)M1_(e)M2_(f)]O₂, theprecursor Ni_(d)M1_(e)M2_(f)(OH)₂ was mixed witty LiOH.H₂O and calcinedat 700° C. for 10 h under oxygen atmosphere.

For example, the metal source can be a spent battery leached orconstituent thereof (e.g. cathode, anode, black mass, slag or mixturesthereof) (e.g. the cathode only, or both the anode and the cathode or ablack mass, etc) leached by the electrochemically generated sulfuricacid.

The leaching metal sulfate solution can contain the metal retrieved fromthe spent battery (e.g. Li, Ni, Co and/or Al and/or Mn). For example,NaOH can be added as a source of pH enhancer to a mixture of metalsulfate(s) for the precipitation of the metal hydroxide(s). Afterprecipitation of the metal hydroxide(s), a mixture of Li₂SO₄ and Na₂SO₄can be recovered as a dissolved species in aqueous solution to beinserted in the membrane electrolyser, and Li₂SO₄ can be converted intoLiOH to react with a metal hydroxide(s) to form a metal oxide(s).

The person skilled in the art would understand that another base couldbe used instead of NaOH. For example, KOH, RbOH, CsOH, Mg(OH)₂, Ca(OH)₂,Sr(OH)₂, or Ba(OH)₂ could be used.

The embodiments of paragraphs [0036] to [00291] of the presentdisclosure are presented in such a manner in the present disclosure soas to demonstrate that every combination of embodiments, when applicablecan be made. These embodiments have thus been presented in thedescription in a manner equivalent to making dependent claims for allthe embodiments that depend upon any of the preceding claims (coveringthe previously presented embodiments), thereby demonstrating that theycan be combined together in all possible manners. For example, all thepossible combination, when applicable, between the embodiments ofparagraphs [0036] to [00291] and the processes of paragraphs [0005] to[0035] are hereby covered by the present disclosure.

The present disclosure has been described with regard to specificexamples. The description was intended to help the understanding of thedisclosure, rather than to limit its scope. It will be apparent to oneskilled in the art that various modifications can be made to thedisclosure without departing from the scope of the disclosure asdescribed herein, and such modifications are intended to be covered bythe present document.

All publications, patents and patent applications are hereinincorporated by reference in their entirety to the same extent as ifeach individual publication, patent or patent application wasspecifically and individually indicated to be incorporated by referencein its entirety. Where a term in the present disclosure is found to bedefined differently in a document incorporated herein by reference, thedefinition provided herein is to serve as the definition for the term.

1. A process for preparing a metal hydroxide for use in the manufactureof a cathode material for lithium ion batteries comprising (i) at leastone metal chosen from nickel and cobalt and optionally (ii) at least onemetal chosen from manganese, lithium and aluminum, said processcomprising: reacting a metal sulfate comprising (i) at least one metalchosen from nickel and cobalt and optionally (ii) at least one metalchosen from manganese, lithium and aluminum with lithium hydroxide andoptionally a chelating agent in order to obtain a solid comprising saidmetal hydroxide and a liquid comprising lithium sulfate; separating saidliquid and said solid from one another to obtain said metal hydroxide;submitting said liquid comprising lithium sulfate to an electromembraneprocess for converting said lithium sulfate into lithium hydroxide; andreusing said lithium hydroxide obtained by said electromembrane processfor reacting with said metal sulfate.
 2. A process for preparing a metalhydroxide comprising (i) at least one metal chosen from nickel andcobalt and optionally (ii) at least one metal chosen from manganese,lithium and aluminum, said process comprising: reacting a metal sulfatecomprising (i) lithium; (ii) at least one metal chosen from nickel andcobalt and optionally (iii) at least one metal chosen from manganese andaluminum with sodium hydroxide and optionally a chelating agent in orderto obtain a solid comprising said metal hydroxide and a liquidcomprising sodium sulfate and lithium sulfate; separating said liquidand said solid from one another to obtain said metal hydroxide;submitting said liquid comprising sodium sulfate and lithium sulfate toan electromembrane process for converting said sodium sulfate and saidlithium sulfate into sodium hydroxide and lithium hydroxide; and reusingsaid sodium hydroxide obtained by said electromembrane process forreacting with said metal sulfate.
 3. (canceled)
 4. The process of claim2, wherein LiOH is substantially selectively crystallized and removedfrom said electromembrane process by evaporative crystallization. 5.(canceled)
 6. The process of claim 2, wherein LiOH is separated fromNaOH by substantially selectively crystallizing LiOH by evaporativecrystallization.
 7. The process claim 1, wherein said solid is aprecipitate comprising said metal hydroxide, said precipitate beingobtained at a pH of about 8 to about
 14. 8-13. (canceled)
 14. A processfor preparing a metal oxide comprising (i) at least one metal chosenfrom nickel and cobalt and optionally (ii) at least one metal chosenfrom manganese, lithium and aluminum, said process comprising: reactinga metal sulfate comprising (i) at least one metal chosen from nickel andcobalt and optionally (ii) at least one metal chosen from manganese,lithium and aluminum with lithium hydroxide and optionally a chelatingagent to obtain a solid comprising a metal hydroxide comprising (i) atleast one metal chosen from nickel and cobalt and optionally (ii) atleast one metal chosen from manganese, lithium and aluminum, and aliquid comprising lithium sulfate; separating said liquid and said solidfrom one another to obtain said metal hydroxide; submitting said liquidcomprising lithium sulfate to an electromembrane process for convertingsaid lithium sulfate into lithium hydroxide; and reusing at least afirst portion of said lithium hydroxide obtained by said electromembraneprocess for reacting with said metal sulfate; reacting at least a secondportion of said lithium hydroxide obtained by said electromembraneprocess with said obtained metal hydroxide to obtain a mixture of metalhydroxides; and roasting said mixture of metal hydroxides to obtain saidmetal oxide.
 15. A process for preparing a metal oxide comprising (i) atleast one metal chosen from nickel and cobalt and optionally (ii) atleast one metal chosen from manganese, lithium and aluminum, saidprocess comprising: reacting a metal sulfate comprising (i) lithium;(ii) at least one metal chosen from nickel and cobalt and optionally(iii) at least one metal chosen from manganese and aluminum with sodiumhydroxide and optionally a chelating agent in order to obtain a solidcomprising said metal hydroxide and a liquid comprising sodium sulfateand lithium sulfate; separating said liquid and said solid from oneanother to obtain said metal hydroxide; submitting said liquidcomprising sodium sulfate and lithium sulfate to an electromembraneprocess for converting said sodium sulfate and said lithium sulfate intosodium hydroxide and lithium hydroxide; separating said lithiumhydroxide and said sodium hydroxide from one another; reusing at least afirst portion of said sodium hydroxide obtained by said electromembraneprocess for reacting with said metal sulfate; reacting at least a firstportion of said lithium hydroxide obtained by said electromembraneprocess with said obtained metal hydroxide to obtain a mixture of metalhydroxides; and roasting said mixture of metal hydroxides to obtain saidmetal oxide. 16-81. (canceled)
 82. The process of claim 1, wherein thechelating agent is chosen from NH₃, NH₄OH, acetylacetone,5-sulfosalicylic acid, and oxalic acid.
 83. The process of claim 1,wherein the chelating agent is chosen from EDTA(ethylenediaminetetraacetic acid) NTA (nitrilotriacetic acid), DCTA(trans-1,2-diaminocyclohexanetetraacetic acid), DTPA(diethylenetriaminepentaacetic acid), and EGTA (ethylene glycolbis(2-aminoethyl ether)-N,N,N′,N′-tetraacetic acid).
 84. (canceled) 85.The process of claim 1, wherein said metal hydroxide is NiCoAl(OH)₂ orNiMnCo(OH)₂.
 86. The process of claim 1, wherein said metal hydroxide ischosen from Ni_(0.8)Co_(0.15)Al_(0.05)(OH)₂,Ni_(0.8)Mn_(0.1)Co_(0.1)(OH)₂ and Ni_(0.6)Mn_(0.2)Co_(0.2)(OH)₂.
 87. Theprocess of claim 14, wherein said metal oxide is of formula LiMO₂, orLi_((1+x))M_((1−x))O₂ for lithium-rich and Li_((1−z))M_((1+z))O₂ forLi-deficient, wherein M is at least one metal chosen from nickel,cobalt, manganese, lithium and aluminum.
 88. The process of claim 1,wherein said metal oxide is chosen from LiNi_(0.33)Mn_(0.33)Co_(0.33)O₂,LiNi_(0.5)Mn_(0.3)Co_(0.2)O₂, LiNi_(0.6)Mn_(0.2)Co_(0.2)O₂,LiNi_(0.8)Mn_(0.1)Co_(0.1)O₂ and LiNi_(0.8)Co_(0.15)Al_(0.05)O₂. 89.(canceled)
 90. The process of claim 1, wherein said lithium hydroxideobtained by said electromembrane process is crystallized before beingreacted with said obtained metal hydroxide to obtain a mixture of metalhydroxides.
 91. (canceled)
 92. The process of claim 90, wherein saidprocess comprises submitting said liquid comprising said sulfate to saidelectromembrane process for converting said sulfate into said hydroxideand to generate sulfuric acid.
 93. The process of claim 92, wherein ananolyte of said electromembrane process is treated by substantiallyselectively precipitating a sulfate therefrom, thereby increasing H₂SO₄concentration.
 94. The process of claim 93, wherein LiOH issubstantially selectively precipitated over sodium hydroxide byevaporative crystallisation. 95-97. (canceled)
 98. The process of claim1, wherein the metal sulfate is obtained from a metal source. 99-102.(canceled)
 103. The process of claim 98, wherein the metal sulfate isobtained by leaching or stripping the metal source withelectrochemically generated sulfuric acid. 104-107. (canceled)
 108. Theprocess of claim 98, wherein the metal source is a spent battery or aconstituent thereof. 109-115. (canceled)
 116. The process of claim 1,wherein sodium hydroxide is used to increase pH and reacted with (a)said metal sulfate comprising (i) said at least one metal chosen fromnickel and cobalt and optionally (ii) said at least one metal chosenfrom manganese, lithium and aluminum; and (b) said lithium hydroxide, toobtain said metal hydroxide.
 117. The process of claim 1, wherein sodiumhydroxide is reacted with said metal sulfate and lithium hydroxide. 118.The process of claim 117, wherein sodium hydroxide is used as a pHenhancer to cause precipitation of said metal hydroxide. 119-258.(canceled)
 259. The process of claim 1, wherein the hydroxide is chosenfrom nickel-cobalt-manganese hydroxides, nickel-cobalt-aluminumhydroxides, lithium-cobalt hydroxides, nickel hydroxides,nickel-cobalt-manganese oxyhydroxides, nickel-cobalt-aluminumoxyhydroxides, nickel oxyhydroxides and lithium-cobalt oxyhydroxides.260-264. (canceled)
 265. The process of claim 1, wherein H₂SO₄ generatedduring the electromembrane process is separated from lithium sulfate,sodium sulfate and/or potassium sulfate through anolyte concentration byselective crystallization of a sulfate monohydrate. 266-277. (canceled)